JPH03215470A - Propionic acid amide derivative, its production and herbicide containing the derivative as active component - Google Patents

Abstract

NEW MATERIAL:The propionic acid amide derivative of formula I [R<1> is group of formula II (R<4> and R<5> are H, halogen or trihalogenomethyl) or formula III (HAL is halogen); R<2> is group of formula IV (X is O or S; R<6> is H or 1-4C alkyl), formula V (R<7> is 1-4C alkyl) or formula VI (R<8> and R<9> are R<7>, 1-4C hydroxyalkyl, 6-10C aralkyl, substituted phenyl or triazolyl or together form an N-containing heterocyclic group); R<3> is H, trihalogenomethyl or group of formula VII (R<10> is R<7> or 6-10C aralkyl)]. EXAMPLE:2-[4-(3-Chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy]-propionic acid (1-acetoxy-1-methoxycarbonyl)methylamide. USE:Useful as a herbicide having low toxicity. PREPARATION:The compound of formula I can be produced by reacting a compound of formula VIII (Ac is acetyl) with a compound of formula IX (M is alkali metal) in the presence of a base.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to the general formula (1): [wherein R' is a group (wherein R4 and R5 are each independently a hydrogen atom,
represents a halogen atom or a trihalogenomethyl group) or a group (in the formula, HAL represents a halogen atom), RZ is a group X-R6 (in the formula, X represents 0 or S, R6 represents a hydrogen atom or a C1 -C4 alkyl group) or a group -OCO-R' (in the formula, R7 represents a C, -C. alkyl group) or a group (in the formula, RI' and R9 each independently represent a hydrogen atom, C, ~C4 alkyl group, 01~C4 hydroxyalkyl group, 06~C1; represents an aralkyl group, an optionally substituted phenyl group or a triazolyl group, or R
8 and R9 together contain a nitrogen atom? (represents a cyclic group) R3 is a hydrogen atom, a trihalogenomethyl group, or a group -C
A propionic acid amide derivative represented by O■R1° (wherein RIG represents a hydrogen atom, a C, -c4 alkyl group, or a C6-C1 aralkyl group), a method for producing the same, and a herbicide containing the same as an active ingredient. Regarding.

Examples of the alkyl groups for R2 and R3 in general formula (1) include methyl group, ethyl group, probyl group, butyl group, isobrobyl group, isobutyl group, etc., and the hydroxyalkyl groups for R8 and R9 include , for example, hydroxymethyl, hydroxyethyl, hydroxybubutyl, hydroxybutyl, etc. Examples of the substituent of the phenyl group include a halogen atom, a lower alkyl group, and the like.

Furthermore, examples of the aralkyl group for R8, R9 and R I O include benzyl, phenethyl, phenylprobyl, phenylbutyl, and the like.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, preferably a fluorine atom and a chlorine atom.

[Conventional technology]

A series of pyridyloxyphenoxy compounds such as 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic acid have been developed as important herbicides in agriculture and horticulture. . These pyridyloxyphenoxy herbicides are safer than the previous phenoxy herbicides, have less impact on useful cultivated plants, and have a strong herbicidal effect. However, these biridyloxyphenoxy herbicides have low selectivity for monocots, cause damage to useful plants such as rice, wheat, and barley, and are not effective against some perennial weeds. Therefore, its application situations and usage were extremely limited.

[Problem to be solved by the invention]

The present inventor has developed a herbicide that maintains the characteristics of these biridyloxyphenoxy herbicides, increases selectivity among monocot plants, and does not cause chemical damage to rice, wheat, or barley. In the course of our research, we discovered a herbicidal compound with very strong activity and good selectivity among propionic acid amide derivatives.

[Means to solve the problem]

According to the present invention, there are provided a propionic acid amide derivative represented by the general formula (1), which is a new compound having a strong herbicidal effect, and its production method and uses.

The compound of the present invention differs from conventionally well-known herbicides in that it contains a probionic acid amide derivative in its skeleton, and has extremely low toxicity to the human body.

The brobionic acid amide derivative represented by the general formula (1) according to the present invention can be produced by the following method.

(Production method A) General formula (2): (wherein, R' is as defined above) and general formula (3): R3-CHO (3) (wherein, R3 is as defined above) ) is reacted with an aldehyde represented by the general formula (4): (wherein Rl,
R3 is as defined above) to obtain a compound represented by
This is further acetylated to form the general formula (5): (wherein, R'l and R3 are as defined above, and AC
represents an acetyl group), and further converts this into the formula: M-X-R' or NHR''R9 (wherein M, R6, RI' and R9 are as defined above). By reacting in the presence of a base, the general formula (1) [wherein R1 and R3 are as defined above, and R2 is -
X-R6 or -NR"R' (wherein R6, R8 and R9 are as defined above)].

(Production method B) The compound represented by the general formula (4) is reacted with a halogenating agent to form a compound represented by the general formula (6): (wherein, Y represents a chlorine atom or a bromine atom, Rl and R
3 is as defined above), and further this is R6-XH, R'COOH or NHR"R" (in the formula,
R6, R7, R8, Rq are as defined above) in the presence of a base to form a compound of the general formula (1): (wherein Rl, R2 and Rq are as defined above)
How to manufacture.

(Production method C) A compound represented by the general formula (2) and Rh-X-CHZCI or Rh
(wherein, Rh and X are as defined above) by reacting with the general formula (1)"
6 (wherein R6 is as defined above and R3 represents a hydrogen atom).

In production method A, the reaction between compound (2) and compound (3) includes hydrocarbons such as habenzene, toluene, xylene, hexane, and liguchin, or esters such as ethyl acetate and butyl acetate, or dimethyl sulfoxide, N ,N-
The reaction can be carried out in various solvents such as aprotic polar solvents such as dimethylformamide, or ethers such as dioxane, tetrahydrofuran, etc., and tetrahydrofuran is preferred. Also, the reaction temperature is 30~
It is desirable to carry out the reaction at 120°C, particularly at 50-100°C. Acetylation of the hydroxymethylamide derivative (4) can be carried out by a conventional method (eg, acetic anhydride in pyridine). The reaction between the obtained compound (5) and an amine, alcohol, or thiol is carried out in a solvent inert to the reaction (e.g., tetrahydrofuran), and if necessary, a base (e.g., butyllithium, lithium diisobutyramide, potassium t-butoxide). ) can be done by adding The reaction temperature is between -20 and 60°C, depending on the base.

The halogenation in Production Method B can be carried out by reacting in thionyl chloride or thionyl bromide at below room temperature to around room temperature, and distilling off the excess amount of the halogenating agent after the reaction. The obtained compound (6) and amine, alcohol, thiol,
For the reaction with carboxylic acid, the reaction is carried out in an inert solvent (e.g., tetrahydrofuran), and if necessary, a base (e.g., an organic base such as triethylamine, pyridine, dicyclohexylamine, or an inorganic base such as sodium carbonate or ammonium carbonate) is added. This can be done by:

Alkylation in production method C uses hydrocarbons such as benzene, toluene, and xylene, or dimethyl sulfoxide,
Bases (e.g., sodium hydroxide, butyl lithium, lithium diisobutylamide, potassium t -butoxide). The reaction temperature is between -20 and 60°C, depending on the base.

After the reaction, the compound of the present invention obtained as described above can be purified using a general purification method, if necessary.

Common purification methods include recrystallization, column chromatography, and preparative thin layer chromatography.

Note that the compound according to the present invention includes optical isomers based on X, Y, and pyridyloxyphenoxypropionic acid, and it goes without saying that all of these are included within the scope of the present invention.

The compounds of the present invention thus obtained have low toxicity to humans and livestock, and have extremely specific and strong growth-inhibiting activity against monocots. This suggests that the compounds of the present invention can be widely used as agricultural chemicals.

When applying the compound of the present invention as a herbicide,
In general, it can be applied in combination with a suitable carrier, such as a solid carrier such as clay or diatom, or a liquid carrier such as water, alcohols, aromatic hydrocarbons, ethers, ketones, and esters. If desired, emulsifiers, dispersants, suspending agents, spreading agents, stabilizers, etc. can be added to provide formulations such as emulsions, wettable powders, granules, and powders. It may be applied in combination with herbicides, various insecticides, fungicides, plant growth regulators, etc.

In practicing the present invention, the concentration of the compound of the present invention can vary over a wide range, but it is generally preferred to use it in the range of 0.5 to Log per 10 ares. When manufacturing the various formulations mentioned above, the active ingredient should be 0.5 to 9
It can be manufactured to contain within the range of 9%.

〔Example〕

Next, the present invention will be explained in more detail with reference to Examples, Test Examples, and Formulation Examples, but it goes without saying that the technical scope of the present invention is not limited by these Examples.

1 H8 14) 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic acid (
Synthesis of 1-acetoxy-1-methoxycarbonyl)methylamide 2-(4-(3-chloro5-trifluoromethyl-
1.08 g of 2-pyridyloxy)phenoxy)propionic acid amide and 552 g of glyoxylic acid monohydrate were dissolved in 50 d of tetrahydrofuran and stirred under reflux for 3 hours. The solvent was distilled off under reduced pressure, methanol 50R1, concentrated sulfuric acid 0.4-
was added and stirred at room temperature for 2 hours. 50 d of water to the reaction mixture
was added, extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate.

20d of pyridine is added to the oil obtained by distilling off the solvent under reduced pressure.
, 0.57 m of acetic anhydride was added, and the mixture was stirred at room temperature for 3 hours.

The solvent was distilled off under reduced pressure, 50 d of water was added, and the mixture was extracted with ethyl acetate.
After washing with water, it was dried over anhydrous magnesium sulfate. The oil obtained by distilling off the solvent under reduced pressure was subjected to pressure ram chromatography in silica gel (n-hexane:ethyl acetate = 3:2).
) to obtain the title compound 910■ as white crystals.

2 human ″20) 2- (4-(3-chloro-5-trifluoromethyl-
2-pyridyloxy)phenoxy)bropionic acid (1
Synthesis of -(N,N-dimethylamino)-1-methoxycarbonyl)methylamide 2- (4- (3-chloro-
Dissolve 500 μl of 5-trifluoromethyl-2-pyridyloxy)phenoxy)brobionic acid (1-acetoxy-1-methoxycarbonyl)methylamide in 15 μl of tetrahydrofuran, and dissolve 0.14 μl of 50% dimethylamine aqueous solution.
- was added and stirred at 60°C for 2 hours. 100 parts of water was added to the reaction mixture, extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. The oil obtained by distilling off the solvent under reduced pressure was subjected to pressure ram chromatography in silica gel (
The mixture was treated with n-hexane:ethyl acetate (1:1) to obtain 450 ml of the title compound as a colorless oil.

3 Hi・Δ・l:+50) 2- (4- (3.5-dichloro-2-pyridyloxy)phenoxy)propionic acid (1-methoxy-1-
Synthesis of trichloromethyl)methylamide 1.64 g of 2-('4-(3.5-dichloro-2-pyridyloxy)phenoxy)propionic acid amide and 1.24 g of chloral hydrate were dissolved in dioxane 50d.
The mixture was stirred under reflux for 5 hours. The solvent was distilled off under reduced pressure, and 50 Id of chloroform and 0.73 ai of thionyl chloride were added. was added, and the mixture was further stirred under reflux for 5 hours. The solvent was distilled off under reduced pressure, and methanol
01 was added, and the mixture was stirred under reflux for 5 hours. The oil obtained by distilling off the solvent under reduced pressure was subjected to pressure ram chromatography in silica gel (n-hexane:ethyl acetate = 3:2) to obtain 520 ml of the title compound in the form of an oil.

4 H8 〇3 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)probionic acid Synthesis of methoxymethylamide Suspend 240 μ of 60% sodium hydride in 15 d of toluene, 1.08 g of 2-(4-(3-chloro-5-trifluoromethyl-2-pyridyloxy)phenoxy)propionic acid amide was slowly added at 70°C.

After stirring at 70°C for 20 minutes, the mixture was cooled to 10°C, 0.34 d of chlorodimethyl ether was added, and the mixture was stirred at room temperature for 3 hours.

50 d of water was added to the reaction mixture, extracted with ethyl acetate, washed with water, and dried over anhydrous magnesium sulfate. The crystals obtained by evaporating the solvent under reduced pressure were subjected to pressure ram chromatography in silica gel (n-hexane:ethyl acetate = 1:1) to obtain the title compound 840■ as a colorless oil.

In addition, by the same method as in Example 1 above, compound numbers 1, 2, 9, 10, 11, 12, 13, 34 were prepared using production method A.
, 39, 40, 44, 45, 51, 56, and 57 were synthesized.

Compound Nos. 5, 6, 7, 15, 16, 17, 18, l9 were prepared using Production Method B in the same manner as in Example 2 above.
, 21, 22, 23, 24, 25, 26, 27, 28,
29, 30, 31, 32, 33, 35, 36, 37, 3
8, 43, 46, 47, 48, 49, 53, 55, 58
, 59, 60, and 61 were synthesized.

In the same manner as in Example 4 above, compounds Nos. 4, 8, 41, 42, 52, and 54 were synthesized using Production Method C.

The structures and physical properties of all the compounds synthesized above are shown in Tables 1 and 2.

Note) Compound numbers 11, 20, 23, 24, 26, 27, 35
Since the melting point and refractive index of compound No. 37 cannot be measured, the absorption data of the nuclear magnetic resonance spectrum is shown below.

Compound 1l Compound 20 Compound 23 δ (CDC1i): δ (CDCh): δ (CDCI:l): 1.6, 1.7 (total3H, both-d)
4.8 (IH, m), 5.6 (18, d), 7.0-7
．． 3 (4}1, m), 7.4-7.8 (2H, m)
, 8.0 (LH, m), 8.2 (IH, m) 1.6, 1.7 (total3H.both-d)2
．． 2(3B, s) , 2.4(3t{, s} ,
3.8, 3.9 (total3}1, both-s) 4
．． 8 (LH, q). 5.4 (IH, d), 7-7.4 (
5B, m), 8 (LH, m), 8.2 (1}1, m) 1.0 to 1.2 (3H, m), 1.6, 1.7 (tot
al3H, both-d), 2.4-2.6 (2H.m
), 3.7, 3.8 (total13H, both-
s), 4.7 (IH, m), Compound 24 Compound 26 Compound 27 Compound 35 (CDCh) di(CDCI3): (CDC13): (CDCl3): 5.3 (1}1, d), 6.9 ~7.3(5}1m),
8.0 (1}1, m), 8.2 (LH, m) 1.6,
1.7 (total3H, both-d) 2.2,2
．． 4 (total3H, both-s) 3.8.3.9
(total3H, both-s) 4.8 (LH, q)
, 5.4 (LH, d), 6.9-7.3 (5H, m),
8 (IH, +a), 8.2 (IH, m) 1.4-1.8 (7H, ++), 2.4-2.8 (
4Hv). 3.7.3.8 (total3H, both
-s), 4.7 (18, +++), 5.3 (18, d)
, 6.9-7.3 (10}1, m), 8.0 (IH, m
), 8.2 (IH, n+) 1.4 to 1.8 (7H, m)
．． 2.5 (IH, +I+), 2.7 (2H, m),
3.6 (2H, m), 3.7, 3.8 (total3H
, both-s), 4.7 (1B, m), 5.3 (
1}1d), 6.9-7.3 (6H, m), 8.0 (IH, m), 8.2 (IH, m) 0.9-1.
26 (6B, m), 1.6 (2}1, compound 37 (CDCI: d), 2.3-3.0 (4H, m), 4.8 (LH, m
), 5.4 (LH, m), 6.9 to 7.3 (5H, m)
, 8.0 (LH, m), 8.2 (LH, m) 0.8 to 2.0 (3H, m), 1.2 to 1.8 (7H,
m). 2.4-2.9 (2H, m), 4.7 (IH, m
), 5.3 (IH, d) 6.6-7.2 (6H, m),
8.0 (lf{, m), 8.2 (IH, m) 1 7. IX7. Field soil was filled in a 1 cm square pot, and after sowing Japanese millet and crabgrass, five loaves of soil were covered, a predetermined dose of the test compound was diluted with water, and IOL per area was treated with the soil. After treatment, the plants were kept in a greenhouse for 20 days, and the herbicidal effect was observed and evaluated according to the following criteria, and the results shown in Table 3 were obtained.

5: Complete withering 4: Major damage 3: Medium damage 2: Minor damage 1: Minor damage 0: Harmless 2 7. 1 x 7. Field soil was filled in a 1 cl square pot, and after sowing golden grass and crabgrass, the plants were covered with 5 m of soil and grown in a greenhouse for 7 days to form two-leaf stage plants. The IOL was diluted and treated per are. After treatment, the plants were kept in a greenhouse for 20 days, and the herbicidal effect was observed and evaluated using the same criteria as in Test Example 1, and the results shown in Table 4 were obtained.

[Test Example 3] (Paddy field, pre-emergence treatment) 7. IX7. Paddy soil was filled in a rectangular pot of I Cll, and the pot was flooded to form a paddy field, and after sowing Japanese millet and Japanese grasshopper, a predetermined dose of the test compound was diluted with water and dripped onto the water surface of the pot using a pipette. After treatment, the plants were kept in a greenhouse for 20 days, and the herbicidal effect was observed and evaluated using the same criteria as in Test Example 1, and the results shown in Table 5 were obtained.

4. 7. IX7. A 1 cm square pot was filled with paddy soil and flooded to make it into a paddy field. After sowing Japanese millet and Japanese grasshopper, they were grown in a greenhouse for 7 days to form two-leaf stage plants, and a predetermined dose of the test compound was added with water. It was diluted and dripped onto the water surface of the pot using a pipette. After the treatment, the plants were kept in a greenhouse for 20 days, and the herbicidal effect was observed and evaluated using the same criteria as Test Example 1, and the results shown in Table 6 were obtained.

1 15 parts by weight of this compound as active ingredients, 65 parts by weight of xylene and polyoxyethylene alkyl allyl ether 2
0 parts by weight were mixed to form a homogeneous solution to obtain an emulsion containing 15% of the active ingredient compound. When using, dilute with water to the specified concentration and spray.

2 40 parts by weight of this compound as an active ingredient, Siegrite 5
5 parts by weight, 2 parts by weight of sodium alkylbenzenesulfonate, and 3 parts by weight of polyoxyethylene alkylaryl ether
Parts by weight were mixed and ground to obtain a permanent agent containing 40% of the active ingredient compound. Before use, dilute with water to the specified concentration and spray.

3I 5 parts by weight of this compound as an active ingredient, 20 parts of bentonite
Parts by weight, 73 parts by weight of clay and 2 parts by weight of sodium dodecylbenzenesulfonate are mixed together, approximately 20 parts by weight of water is added, and the mixture is kneaded in a kneader, then granulated through a granulator, and then dried and sized to form an effective product. Granules containing 5% of the ingredients were obtained.

Claims (1)

[Claims] 1. General formula (1) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 is a group ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R ^4 and R^5 each independently represent a hydrogen atom, a halogen atom, or a trihalogenomethyl group) or a group ▲ has a mathematical formula, chemical formula, table, etc. ▼ (in the formula: HAL represents a halogen atom) , R^2
is a group -X-R^6 (in the formula, X represents O or S, and R^6 represents a hydrogen atom or a C_1 to C_4 alkyl group) or a group -OCO-R^7 (in the formula, R^7 represents a C_1 to C_4 alkyl group)
or group ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^8 and R^9 are each independently a hydrogen atom, a C_1-C_4 alkyl group, a C_1-C_4 hydroxyalkyl group, a C_6-C_1_0 aralkyl group) , represents an optionally substituted phenyl group or triazolyl group, or R^8 and R^9 together represent a heterocyclic group containing a nitrogen atom) R^3 is a hydrogen atom, a trihalogenomethyl group or group -C
O_2R^1^0 (In the formula, R^1^0 represents a hydrogen atom, a C_1 to C_4 alkyl group, or a C_6 to C_1_0 aralkyl group)]
A propionic acid amide derivative represented by 2. The compound according to claim 1, wherein the heterocyclic group is a piperidino group, a morpholino group, a pyrrolidino group, a pyrazolyl group, an imidazolyl group or a triazolyl group. 3. General formula (1)′ ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1)′ [(In the formula, R^1 and R^3 are as defined above,
R^2 is -X-R^6 or ▲ has a mathematical formula, chemical formula, table, etc. ▼ (in the formula, R^6, R^8 and R^9 are as defined above)] To produce a compound Method, formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1 and R^3 are as defined above, and A
_c represents an acetyl group) and the formula: M-
X-R^6 (where M is an alkali metal atom, X and R^
6 is as defined above) or formula: NHR^8R
^9 (wherein R^8 and R^9 are as defined above) in the presence of a base. 4. General formula (1)'' ▲There are mathematical formulas, chemical formulas, tables, etc.▼(1)'' [In the formula, R^1 is as defined above, and R^2 is -X
-R^6, (wherein R^6 is as defined above) R
^3 represents a hydrogen atom] is a method for producing a compound represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (in the formula, R^1 is as defined above), a compound represented by a base is In the presence of the formula: R^6-X-CH_2Br or R^6-X-CH_2
A method characterized by reacting with Cl. 5. General formula (1): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R^1, R^2, and R^3 are as defined above). Herbicide contained as an ingredient.