JPS6272647A - Diphenyl ether derivative and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [X is H, Cl or F; Y is H or NO2; Z is formula V (Q is CN, carboxyl or carboxylic acid derivative), formula VI (R is H, lower alkyl, lower alkenyl, lower alkynyl, cycloalkyl, aralkyl, alkoxyalkyl or alkali metal, e.g. Na or K, etc.]. EXAMPLE:3-(2-Chloro-4-trifluoromethylphenoxy)-alpha,alpha-dimethylphen ylacetonitrile. USE:A herbicide suitable for controlling weds growing in paddy field, upland field, orchard and uncultivated land. PREPARATION:A compound expressed by formula II is reacted with a halogenating agent in the presence of a radical reaction initiator to form a compound expressed by formula III (hal is Cl or Br), which is then reacted with NaCN to give a compound expressed by formula IV. The resultant compound expressed by formula IV is then reacted with CH3I in the presence of a base to afford the aimed compound expressed by formula I [Y is H; Z is formula V (Q is CN)].

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel diphenyl ether derivatives and their uses. Specifically, general formula (I) [wherein,
(wherein Q represents a cyano group, carxyl group, or carboxylic acid derivative) or the formula -CH2COOR (wherein R is a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, an aralkyl group) , an alkoxyalkyl group, an alkylthioalkyl group, or an alkali metal such as sodium or potassium). The present invention relates to a herbicide characterized by containing a novel diphenyl ether derivative represented by the following formula and at least one of these compounds as an active ingredient.

An object of the present invention is to provide a novel herbicide which is industrially advantageously produced and which is extremely useful in practice.

As a result of synthesizing various diphenyl ether derivatives and examining their herbicidal activity, the present inventors discovered that the diphenyl ether derivative represented by the above general formula (I) has extremely excellent characteristics as a herbicide, and completed the present invention. I ended up doing it. That is, the compounds of the present invention have excellent herbicidal activity and are therefore suitable for controlling weeds growing in rice fields, fields, orchards, and non-agricultural lands. The compound of the present invention is
In particular, when spraying on the field surface, the foliage surface of the plant body, or submerged water just before weeds emerge or during the growing season,
Extremely high weed control effect can be obtained.

Also, when the compound of the present invention is mixed into soil, an extremely excellent weed control effect can be obtained.

The applied dosage of the compound of the present invention should be 0.01 to 1 hectare per hectare.
(limited to fc#5 to 9) or as a selective herbicide in cultivated fields of rice, corn, wheat, barley, sugarcane, soybeans, peanuts, sunflowers, cotton, beet potatoes or fruit trees by applying suitable application methods. It can be used as .

Moreover, by increasing the amount of the applied drug, it can be applied as a non-selective herbicide.

The diphenyl ether derivative of the present invention can be produced, for example, according to the following reaction formula.

(II) ([1)(mV) (V) (M) (■) (■) (IX) (V') (I:R=1() (■(I:R=H) (in the formula , symbols are as above), and hat represents a chlorine atom or a bromine atom) Al 3-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethylzenylacetonitrile A2 3-( 2-chloro-6-fluoro-4-trifluoromethylphenoxy)-α,α-dimethyl-phenylacetonitrile A33-(2-chloro-4-trifluoromethylphenoxy)-α,α-tumethyl-6-nitrophe Enylacetonitrile A43-(2-chloro-4-trifluoromethylphene,
3-(2,6-dichloro-4-trifluoromethylphenoxy)-α,α-dimethylphenylacetic acid A6-3-(2-chloro-4-trifluoromethyl phenoxy)-α,α-dimethyl-6-nitrophenylacetic acid boiled 7 3-(2,6-dichloro-4-trifluoromethylphenoxy)-α,α-dimethyl-6-nitrophenylacetic acid A33-(2-chloro-4 -trifluoromethylphenoxy)-α,α-dimethylphenylacetic acid methyl ester A93-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethylphenylacetic acid 2-methoxy-
Ethyl ester AIO3-(2-chloro-4-trifluoromethylphenoxy)-α,α-tumethyl-6-nitrophenylacetic acid ethyl ester black 113-(2-chloro-6-fluoro-4-trifluoromethylphenoxy)-α , α-dimethyl-6-nitrophenyl acetic acid methylthiomethyl ester Al2N-butyl-N-methyl-3-(2-chloro1:l
-4-)-trifluoromethylphenoxy)-α,α-dimethyl-6-nitrophenylacetamide A13N-Methyl-3-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethyl-6-nitrophe enylacedoamito&14 N-methyl-3-(2
-chloro-4-trifluoromethylphenoxy)-α,
α-dimethyl-6-ditroatrophenylanilide N,N-dimethyl-3-(2,6-dichloro-4-trifluoromethylphenoxy)-α,α-dimethyl-phenylacetamide A16 N-ethyl-3-( 2-chloro-4-trifluoromethylphenoxy)-α,α-dimethyl-phenyl-acetamide 417N, N-tetramethylene-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethyl-6
- Nidrophenylacetamide 41B Sodium 3-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethyl-phenylacetate l619 Potassium 3-(2-chloro-4-trifluoromethylphenoxy)-α,α -dimethyl-phenylacetate 20 sodium 3- (2,6-dichloro-4-
trifluoromethylphenoxy)-α,α-dimethyl-phenylacetic acid A21 3- (2-chloro-4-trifluoromethylphenoxy)-6-nitrophenylacetic acid &22 3-
(2,6-dichloro-4-trifluoromethylphenoxy)-6-nitrophenyl acetic acid A23 3- (2-chloro-6-fluoro-4-trifluoromethylphenoxy)-6-nitrophenyl acetic acid A24 3- (2 -chloro-4-trifluoromethylphenoxy)-6-nitrophenylacetic acid methyl ester boiled 253-(2-chloro-4-trifluoromethylphenoxy)-6-nitrophenylacetic acid ethyl ester A263-(2-chloro-4- Trifluoromethylphenoxy)-6-nitrophenyl acetic acid isoprobyl ester.

A273-(2-chloro-4-trifluoromethylphenoxy)-6-nitrophenyl acetic acid cyclohexyl ester 28 Sodium 3-(2-chloro-4-trifluoromethylphenoxy)-6-nitrophenyl acetate 29 Potassium 3- (2-chloro-4-trifluoromethylphenoxy)-6-nitrophenylacetic acid l630 Sodium 3- (2,6-dichloro-4
-trifluoromethylphenoxy)-6-nitrophenylacetic acid 431 Sodium 3-(2-chloro4-6-fluoro-4-trifluoromethylphenoxy)-6-nitrophenylacetic acid 432 Potassium 3-(2-chloro-6-fluoro -4
-trifluoromethylphenoxy)-6-nitrophenyl acetic acid The active ingredient compounds in the following synthesis examples, examples, and test examples are all indicated by the above compound number (A).

Next, the method for producing the compound of the present invention represented by the general formula (I) will be explained in detail by giving a synthesis example.

Synthesis Example 1 2-chloro-4-) IJ fluoromethylphenyl 3-
Methyl phenyl ether 57.4II and N-bromosuccinimide 36.0.9 were heated under reflux in 400 carbon tetrachloride while benzoyl oxide 1,5
II was added and heated under reflux for 4 hours. After cooling, the solid matter was removed from the furnace, the furnace liquid was washed three times with water, and after drying with sodium sulfate,
The solvent was distilled off under reduced pressure to obtain crude 3-bromomethylphenyl 2-chloro-4-)IJ fluoromethylphenyl ether t-70,4N. and (7) crude '& 3-bromomethylphenyl 2-chloro-4-trifluoromethylphenyl ether 36.69 and sodium cyanide 7.
4I was added to a mixed solvent of 20 ml of water and 80 ml of ethanol, and heated under reflux for 5 hours with stirring. The solvent was distilled off under reduced pressure, toluene and water were added to the resulting residue, and the organic layer was separated.

The organic layer was washed with an aqueous solution of IJ carbonate and then with water, dried over magnesium sulfate, and then the solvent was distilled off under reduced pressure. The obtained oily substance was distilled under reduced pressure, and the boiling point was 196.
18.8 % of 3-(2-chloro-4-trifluoromethylphenoxy)-phenylacetonitrile was obtained at ~198° C. 72 w+Hg. This 3-(2-chloro-4-trifluoromethylphenoxy)-phenylacetonitrile6.
2I and 11.4 g of methyl iodide were added to 30 rnl of dimethyl sulfoxide, and while stirring while cooling to 10-15°C in a water bath, 4.0 g of potassium hydroxide was added. It was added to OIf 1 in 4 portions. After the addition, the mixture was heated to 40°C, stirred for 4 hours, and allowed to cool to room temperature.

Toluene and water were added to separate the organic layer. The obtained organic layer was washed with an aqueous sodium carbonate solution and water in that order, dried over sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was distilled under reduced pressure to give 3=(2-chloro-4-
5.1 N of trifluoromethylphenoxy)-α,α-dimethylphenylacetonitrile (compound 41) was obtained as an oil.

Elemental analysis CHN C1 Analysis value 59.84 4.17 4.00 10.56
Calculated value 60.10 3.86 4.12 10.44
(as C1,H,, ONCpi) NMR (CDCt,) δ1.71 (6H,s), 6.7
~7.7 (7H, m) Synthesis Example 2 3-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethyl-phenylacetonitrile (compound 1) obtained in Synthesis Example 1 3.4N and potassium hydroxide 2.011 water 1.5- and 2-methoxyethanol 9
ml of the solution, and after heating and refluxing for 10 hours with stirring, the solvent was distilled off under reduced pressure.

Toluene and water were added to the obtained residue, the aqueous layer was separated, and the aqueous layer was washed with toluene. The resulting water bath solution was neutralized with concentrated hydrochloric acid and then extracted with ethyl acetate.

The ethyl acetate layer was washed with water 13 times, dried with sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was treated with silica gel column chromatography (developing solvent: dichloromethane) to obtain 3-(2-chloro-4-trifluoromethyl-
phenoxy)-α,α-dimethylphenylacetic acid (Compound 164) 2.71 was obtained as white crystals.

Elemental analysis CHC1 Analysis value 56.55 4.35 10.22 Calculated value 5
6.92 3.93 9.88 (C4, H4403C
tF,) NMR (CDCt3) δ1.60 (6H, a), 6. '
l~7.7 (7H, m), 11.42 (IH, haze) Synthesis Example 3 3-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethylphenyl obtained in Synthesis Example 1 Acetonitrile (compound AI) 1.711 was dissolved in 10 g of dichloromethane, stirred in a water bath while keeping the reaction temperature below 3°C, 0.4 g of nitric acid was added, and concentrated sulfuric acid was added.
．． After dropping 41 nl over 1 hour, the reaction temperature was increased to 15 ml.
℃ and stirred for 15 hours.

Add cold water IQ+++J and then add 10ml of dichloromethane.
was added and extracted. The organic layer was washed with saturated brine and dried over sodium sulfate, and then the solvent was distilled off at normal pressure. The resulting residue was treated with 70 lysyl and then silica gel column chromatography (developing solvent: dichloromethane).
4-) IJ fluoromethylphenoxy)-α,α-dimethyl-6-nitrophenylacetonitrile (compound &
3) 1. Oj9 was obtained as a slag-like substance.

Elemental analysis CHN C1 Analytical value 52.59 2.96 7.63 9.04 Calculated value 53.07 3.14 7.28 9.21 (C47
H4203N2CtF3) NMR (CDCt,
) δ1.88. (6H, s), 6.8-8.1 (6
H, m) Synthesis Example 4 1.8.9 of 3-(2-chloro-4-trifluoromethylphenoxy)-α,α-dimethyl-phenylacetic acid (compound 4) obtained in Synthesis Example 2 was added to Synthesis Example 3 The nitration reaction and subsequent post-treatment were carried out in the same manner as 3-(2-/Rolow 4-)9fluoromethylphenoxy)-α,α-dimethyl-6-nitretrophenylacetic acid compound 46)0 .9.
9 was obtained as pale yellow crystals.

Elemental analysis CHN C1 Analysis value 49.97 3.06 3.82 8.51 Calculated value 50.57 3.25 3.47 8.78 (C
1, Hl, 05NC2F,) NMR (CDC1s
) δ1.65 (6H, s), 6.6 to 8.1 (6H,
m ), 10.15 (I1, m) Synthesis Example 5 2- / C1O+ 4 + ) +7 Fluoromethylphenyl 3-methylphenyl ether 57. l and N-promoscine iodine36. Ojl carbon tetrachloride 4001
Penzoylno mother oxide 1.5.9 was added to the mixture while heating under reflux in a vacuum cleaner, and the mixture was heated under reflux for 4 hours. After cooling, the solid matter was removed from the oven, and the solution was washed three times with water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure to obtain crude 3-bromomethylphenyl 2-chloro-4-trifluoromethyl. Phenyl ether 70.4.9 obtained. Konokorasu 3-bromomethylphenyl 2-chloro-4-trifluoromethylphenyl ether36.6.9 and sodium cyanide7.
4ji was added to a mixed solvent of 201 d of water and 80 ml of ethanol, and heated under reflux for 5 hours with stirring. The solvent was distilled off under reduced pressure, toluene and water were added to the resulting residue, and the organic layer was separated. This organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution and water in that order, and dried over magnesium sulfate.
The solvent was removed under reduced pressure. The obtained oily substance was distilled under reduced pressure to obtain 9.4 g of 3-(2-chloro-4-trifluoromethylphenoxy)-phenylacetonitrile having a boiling point of 196-198°C/2■Hg. This 3-(2-chloro-4
-trifluoromethylphenoxy)-phenylacetonitrile 12. (1 is 5.0 g of water containing 6.0 g of potassium hydroxide)
ml and 39 ml of ethanol, and after heating under reflux for 4 hours, the solvent was distilled off under reduced pressure. 50 ml of water was added to the obtained residue to form a solution, and then concentrated hydrochloric acid was added to neutralize it. The precipitated solid was washed thoroughly with cold water and air-dried. The resulting crude 3-(2-chloro-4-trifluoromethylphenoxy)-phenylacetic acid is recrystallized from a mixed solvent of benzene, ether, and n-hexane. :
, 6.7 g of 3-(2-chloro-4-trifluoromethyl-7enoxy)-phenylacetic acid were obtained as white crystals. 1.7 g of this 3-(2-chloro-4-trifluoromethylphenoxy)-phenylacetic acid was added to 1 ml of dichloromethane.
While keeping the reaction temperature below 3°C in a water bath, add 0.4 g of fuming nitric acid under stirring, and then add concentrated sulfuric acid to 0.4 g.
．． After dropping 4 rnl over 1 hour, the reaction temperature was increased to 15 rnl.
℃ and stirred for 15 hours. Cold water 10mA! was added, and then 10 mA' of dichloromethane was added for extraction. The obtained organic layer was washed with saturated brine, dried over sodium sulfate, and then the solvent was distilled off at normal pressure. The residue was treated with Florisil and then silica gel column chromatography (developing solvent: dichloromethane) to obtain 3-(2-chloro-4-trifluoromethyl-phenoxy)-6-nitrophenyl acetic acid.
．． 91 was obtained as pale yellow crystals.

Elemental analysis CHN C1 Analysis value 47,51 2.35 4.08 9.61 Calculated value 47,96 2.41 3,73 9.44 (C7
5H905NCtF3) NMR (CDC13) δ3.98 (2H,s), 6
．． 7-8.2 (6H, m), 9.5 (IH+br,
s) When the compound of the present invention is applied as a herbicide to rice fields, fields, non-agricultural land, etc., it can be formulated with a solid or liquid carrier, such as an emulsion or a wettable powder, by applying a formulation method commonly used for agricultural chemical formulations. It is preferable to formulate the drug into various dosage forms such as powder, granules, and floaglu. At that time, emulsifiers, spreading agents, various surfactants for other purposes, and other herbicides and agricultural chemicals other than herbicides to expand the range of action, such as insecticides, fungicides, Insecticides, plant growth regulators, fertilizers, etc. can also be mixed.

Next, examples of typical dosage forms will be given. “Part” in the description
indicates parts by weight.

Example 1. 50 parts of this compound, 10 parts of diatom, 35 parts of clay, 3 parts of sodium polyoxyethylene alkyl allyl ether sulfonate, and 2 parts of sodium alkylnaphthalene sulfonate are mixed and pulverized to obtain 50% of the active ingredient compound as an irrigation agent.
Obtain the water-containing agent.

When using, dilute with water to the specified concentration and spray.

Example 2. Emulsion 15 parts of this compound, 70 parts of xylene, 7 parts of isophorone,
? 8 parts of dioxyethylene alkyl allyl ether are mixed to form a homogeneous solution to obtain an emulsion containing 15 parts of the active ingredient. When using, dilute with water to the specified concentration and spray.

Example 3. Granules: Mix 5 parts of the present compound, 20 parts of bentonite, 73 parts of clay, and 2 parts of sodium dodecylbenzenesulfonate, add about 20 parts of water, knead with a mixer, and then granulate with a granulator. Then, the mixture is dried and sized to obtain granules containing 20 grams of the active ingredient.

In order to demonstrate the herbicidal effects of the compounds of the present invention, some representative test examples will be given and explained in more detail.

Test Example 1 Pre-germination soil treatment A pot with an area of 325 i was filled with volcanic ash soil, and corn (Zea mays) and wheat (Triticum) were grown.
aestivum), rice (Oryza 5ativa)
), soybean (Glycine max), cotton (Gos
sypium hirsutum) %) Mado (L
Chrysanthemum coronar
ium), Digitalia sangu
inalis), Golden millet (Echinochloa
eras-galli), Polyg.
onumnodosum), Amarant
hus retroflexus), spelichz (
Portulaca oleracea), Shiroza (C
henopodium album), Ichibi (Abut
Seeds of Ilon theophrasti), Sida 5pinosa, Ipomoea purpurea, and Xantium strumarium were sown, and immediately after that, seeds prepared according to Example 1 were sown. The irrigation agents containing the compounds of the invention were diluted with water equivalent to 100,017 ha in doses of the active ingredient equivalent to 4.0, 2.0, and 1.0 kg per hectare and sprayed onto the soil surface using a sprayer. Three weeks after chemical treatment, the herbicidal effect and chemical damage to the crops were visually observed, and the results were expressed on an 11-level index from 0: no effect or chemical damage to 10: complete withering.
Shown in 1.

Test Example 2 A pot with foliage contact treatment area of 325 crn2 was filled with volcanic ash soil, seeds of plants similar to Test Example 1 were sown, covered with about 1 crn of soil, placed in a greenhouse, and grown for 10 days. An irrigation agent containing the compound of the present invention prepared in accordance with the above method was diluted with water equivalent to 100,017 ha in an amount of the active ingredient equivalent to 4.0, 2.0, 1.0' kg per hectare, and a sprayer was used. It was sprayed. Three weeks after the drug treatment, an investigation was conducted using the same criteria as in Test Example 1, and the results are shown in Table 2. 11. Test Example 3 Leaf contact treatment (low dose test) Area 150cW
? Fill pots with volcanic ash soil and grow corn (Zea
mays), wheat (Triticum aesti)
vum), rice (Oryza 5ativa), soybean (Glycine max), tomato (Lycoper
sicon esculentum), shungiku (C
hrysanthemumeorortar lum)
%Digitalia sanguina
lis), Golden millet (Echinochloa cr
us-galli), Japanese knotweed (Polygon)
um nodosum), Shiroza (Chenopod)
ium album), Ichibi (Abutilon)
theophrasti), Ona fir (Xanthiu)
mstrumallum) 9 seeds were sown, covered with about 1 m of soil, placed in a greenhouse, and grown for 10 days.
A hydrating agent of the compound of the present invention prepared according to
1000 doses equivalent to 0.125゜0.063kg
It was diluted with water equivalent to 1/ha and sprayed using a sprayer. Three weeks after the drug treatment, an investigation was conducted using the same criteria as Test Example 1, and the results are shown in Table 3.

Test Example 4 Flooded soil treatment (before weed emergence) Paddy soil was filled in a pot with an area of 80 i, and Echinochlo
a crus-galli)% Monoch
oriavaginalis), Am.
mannia multiflora) and firefly seeds were mixed into the soil at about 2 crn of the surface layer, and water worms
Tubers of P. yperus 5erotinus and paddy rice at the two-leaf stage were each transplanted to two locations, and the water depth was maintained at 3 crn. After 3 days, the compound of the present invention was added to a hydrating powder prepared according to Example 1 at a rate of 4.0 and 2.0 per hectare.

A dose corresponding to 1.0 and 0.5 kg was administered in water. Three weeks after the chemical treatment, the herbicidal effect and chemical damage to paddy rice were investigated using the same criteria as Test Example 1.

The results are shown in Table 4.

Test Example 5 Flooded soil treatment (after weed emergence) Area 80 crn
Paddy soil was filled in a pot of No. 2, weeded paddy rice according to Test Example 4 was placed in a greenhouse, and after growing for 10 days, an irrigation agent containing the compound of the present invention prepared according to Example 1 was added as an active ingredient. per hectare, 4.0, 2.0, 1.0,
0.5, 0.25, 0.125.

A dose corresponding to 0.063 kilograms was administered in water. Three weeks after the chemical treatment, herbicidal effects and chemical damage to paddy rice were investigated using the same criteria as Test Example 1. The results are shown in Table 5.

Claims (1)

[Claims] 1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X represents a hydrogen atom, a chlorine atom, or a fluorine atom, and Y represents a hydrogen atom or It represents a nitro group, and Z is the formula -C (
CH_3)-Q (in the formula, Q is a cyano group, a carboxyl group,
or a carboxylic acid derivative) or the formula -CH_2COO
R (wherein R represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, an aralkyl group, an alkoxyalkyl group, an alkylthioalkyl group, or an alkali metal such as sodium or potassium). ] A novel diphenyl ether derivative compound represented by 2) General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, X represents a hydrogen atom, chlorine atom, or fluorine atom, Y represents a hydrogen atom or a nitro group, and Z is the formula -C (
CH_3)-Q (in the formula, Q is a cyano group, a carboxyl group,
or a carboxylic acid derivative) or the formula -CH_2COO
R (wherein R represents a hydrogen atom, a lower alkyl group, a lower alkenyl group, a lower alkynyl group, a cycloalkyl group, an aralkyl group, an alkoxyalkyl group, an alkylthioalkyl group, or an alkali metal such as sodium or potassium). ] A herbicide characterized by containing a novel diphenyl ether derivative represented by the following as an active ingredient.