JPS62174069A - Pyridine derivative, production thereof and herbicide - Google Patents

Abstract

NEW MATERIAL:A compound shown by formula I (W is O or S; X is H, alkyl, alkoxymethyl, haloalkyl, benzyl, phenyl, pyridyl, etc.,; Y is O, S, monosubstituted C atom, etc.,; R is H, dialkylimino, alkyl, alkenyl, alkynyl, etc.,; R<1> is alkyl; R<2> is alkyl or cycloalkyl; R<3> is halogen, alkyl, etc.,) and an optical isomer thereof. USE:A herbicide. PREPARATION:A compound shown by formula II is subjected to ring formation with an aqueous solution of an alkaline (earth) metallic hydroxide or to ring formation in an inert solvent in the presence of phosphorus oxychloride, etc., or to ring formation by the use of a dehydrating reagent such as dicyclohexylcarbodiimide to give a compound shown by formula I.

Description

[Detailed description of the invention] The present invention relates to general formula (I): [In the formula, W represents an oxygen atom or a sulfur atom.

Or a hydrogen atom, a lower alkyl group having 1 to 4 carbon atoms, or a lower alkoxymethyl group having 1 to 4 carbon atoms.

Lower alkylthiomethyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
4 lower haloalkyl group, lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, benzyl group, or optionally substituted phenyl group or pyridyl group (this substituent includes a lower alkyl group having 1 to 4 carbon atoms, represents a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group).

Y is an oxygen atom, a sulfur atom, a monosubstituted nitrogen atom (this substituent includes a lower alkyl group having 1 to 4 carbon atoms, a carbon number 1
to 4 lower alkoxy groups, lower alkoxycarbonylamino groups having 1 to 4 carbon atoms, or optionally substituted phenyl groups or pyridyl groups (such substituents include lower alkyl groups having 1 to 4 carbon atoms, lower alkyl groups having 1 to 4 carbon atoms, -4 lower alkoxy group, halogen atom, nitro group, cyano group or trifluoromethyl group). ), is a di-substituted carbon atom (these di-substituents are each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, a 5 carbon atom -6 cycloalkyl group or optionally substituted phenyl group or pyridyl group (this substituent has 1 to 4 carbon atoms)
lower alkyl group, lower alkoxy group having 1 to 4 carbon atoms,
halogen atom.

Indicates a nitro group, cyano group or trifluoromethyl group. ) Furthermore, the di-substituents can be combined to form a base, and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a lower alkyl group having 1 to 3 carbon atoms. ) represents.

R is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such substituents include a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, and a lower alkyl group having 1 to 3 carbon atoms; 3-6 herocycloalkyl group, carboxyl group, lower alkoxy carbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, tri-lower alkylammonium group or optionally halogen atom, carbon number 1-4 lower alkyl group, carbon number 1-4
represents a phenyl group which may be substituted with a lower alkoxy group or a nitro group. ), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (as the substituent).

It represents a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, two lower alkoxy groups having 1 to 3 carbon atoms, or a phenyl group. ).

A lower alkynyl group having 2 to 5 carbon atoms, an oxacycloalkyl group having 5 to 6 carbon atoms, a mono-, di-, or trihaloalkenyl group having 2 to 5 carbon atoms, a haloalkynyl group having 2 to 5 carbon atoms, and a glycidyl group.

1 from an alkylthioalkyl group, a sicummonium having 5 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms;
Represents a discovered cation.

R1 represents a lower alkyl group having 1 to 4 carbon atoms.

R1 is a lower alkyl group having 1 to 4 carbon atoms or 5 carbon atoms
~6 cycloalkyl group.

Further, R' and R'' can be taken together to form a term, and represent a cycloalkyl group having 5 to 6 carbon atoms, which may be substituted with a lower alkyl group having 1 to 3 carbon atoms.

R" is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or
4 alkylthio group, phenoxy group, haloalkyl group having 1 to 4 carbon atoms, haloalkoxy group having 1 to 4 carbon atoms, or alkylsulfonyl group having 1 to 4 carbon atoms. ] or an optical isomer of the derivative (provided that R'' and R1 are not the same), their production method, and the derivative or the optical isomer of the derivative (provided that
This invention relates to a herbicide containing as an active ingredient (when ul and R' are not the same).

The compound of the present invention is a novel compound that has not been described in any literature and has excellent physiological activity as a herbicide.

In the past, it has been generally pointed out that the economic cost of using herbicides depends on the amount of active ingredient treated per unit area. Research into compounds that exhibit high herbicidal effects at low doses has been continued for many years, and the compounds of the present invention have significantly higher herbicidal effects than conventional herbicides. The present inventors have found that the present invention has selectivity for plants of the family 9, such as soybeans, and is practically useful, leading to the completion of the present invention.

In other words, the compound of the present invention can significantly reduce the amount of active ingredient treated per unit area compared to these conventionally known compounds, and its economic effect is extremely superior to that of conventional herbicides. It can be said to be a revolutionary herbicide that can significantly reduce the risk and risk of environmental pollution caused by applying large amounts of chemicals.

The compound (1) of the present invention represented by the general formula CI) can be easily prepared by the following reaction.

Anti-yaku formula 1 (In the formula, W, Alkali metal hydroxides such as sodium oxide, potassium hydroxide, magnesium hydroxide, etc. are heated to a temperature between room temperature and 100°C in an aqueous solution of alkaline earth metal hydroxide at a concentration between 1X and 50X. Accordingly, the compound of the present invention Q) (R= Na, K, Mg, etc.)
is obtained.

By neutralizing this with a mineral acid such as hydrochloric acid or sulfuric acid, the compound of the present invention (CI) (R=H) can be obtained.

When this is treated with ammonia and organic amine, 9
Compound (1) of the present invention (R=ammonium.

organic ammonium cation) can be obtained.

The compound (1) of the present invention can be obtained by esterifying the compound (1) (RmH) of the present invention with various alcohols ROH corresponding to R in an acid catalyst.

Alternatively, the compound of the present invention (D
The compound (I) of the present invention can be obtained by obtaining (Rm +:a,)fc and further transesterifying it with various alcohol ROMs corresponding to R.

The raw material pyridine derivative (IF) (R=H) can be synthesized according to the synthetic route of [Method A] below.

([[[) (,V)(V)
(Vl) 0 (where W, X,
Y, R', R'' and Rm have the same meanings as above.) Synthesis, page 902, published in 1983 (5
Synthesis 902 (19a s)), Chemical Levies, 161 pages, published 1964 (Ohe
m.

Rev, 161 (1964)), Chemical-7/)
”-Pharmacical, Bulletin, Volume 26, 12
01 page, published in 1978 (Ohem, pharm,
Compound (1111) (Y =
carbonyl group) can be synthesized in high yield. Also, Journal of the American Chemical Society, Volume 73, Page 4580, published in 1951 (Journa
l of the m*rican Chemical
5ociety L3L4 380 (1951)),
Journal of the American Chemical Society, vol. 74, p. 1489, published in 1952.
al of the American Ohemi-
cal 5ociety 74 1489 (1952
)), compound (III) (Y-oxygen atom) and ethoxymethylene ogizaloacetate in a suitable solvent (for example, diethyl ether, ethanol, acetic acid).

benzene, etc.), pyridine-2.3
-Dicarboxylic acid diester α) (Y=acid! atom) is obtained in high yield.

The corresponding dicarboxylic acid form (V) is obtained by treating the diester form (IV) (Y = oxygen atom) with a water-alcoholic solution containing 2 equivalents or more of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. (Y = oxygen atom) is obtained.

Alternatively, the diester (IV) (Y = oxygen atom) is reduced using a metal hydride such as sodium borohydride in an appropriate solvent, preferably diethyl ether, methanol or water, and the resulting compound is subjected to appropriate dehydration. agent,
Preferably, the compound av) (Y = R
″-〇-R′) can be synthesized.

Diester body (IV) (Y = R' -C! -R
' ) with a water-alcoholic solution containing 2 equivalents or more of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or diester form (M)
By treating (Y=R″-0-R”) with a mineral acid such as sulfuric acid, the corresponding dicarboxylic acid form (V) (y = R”
-0-, R'') is obtained.

This can be achieved by heating the dicarboxylic acid (V) obtained as described above with anhydrous vinegar, trifluoroacetic anhydride, etc. to a temperature between room temperature and reflux temperature, preferably between 60 and 100°C. An acid anhydride (Vl) is obtained. Acid anhydride (Vi) is purified by α in an inert solvent (e.g. acetonitrile, acetone, methylene chloride, pyridine, picoline, etc.).
A carboxylic acid amide derivative (nHR-a) can be obtained by reacting with a carboxylic acid amide derivative (nHR-a). Carboxylic acid amide derivative (II') which is an isomer (R=H
) may be produced as a by-product.

(In the formula, W, X, Y, R, R', R" and R1 have the same meanings as above.) Grainite formula 2 (In the formula, W, X, Y, R, R', R"? ? and R1 have the same meanings as above.) In other words, the pyridine derivative ([) (R ester or ethyl), etc., may be dissolved in phosphorus oxychloride or phosphorus pentachloride in an inert solvent such as benzene, hexane, or ether, if necessary. The compound C of the present invention can be prepared by treating with sodium hydride, etc.
I) (R=ester or ethyl) can be obtained.

This invention compound (I) (R ester or ethyl)
was hydrolyzed) 9 By carrying out esterification, transesterification, etc. as shown in reaction formula 1, the compound C of the present invention
I).

The raw material pyridine derivative (If) (R ester or ethyl) can be synthesized according to the synthetic route of [Method B] in r.

(iW) [Method B-2] α) (In the formula, W, ethyl) is the corresponding diester (1'i') (R
= Ethyl) half-water splitting reaction or acid anhydride ('4)
Kill in synthesis by methanol or ethanol decomposition.

Compound (W) (R = methyl or ethyl) is converted into an acid chloride with thionyl chloride or the like, or converted into an active ester with jrl chloroformate or the like, and then treated with α-aminoamide (Ml) to form the compound ( I[)(R
= methyl or ethyl). Alternatively, by stirring the acid anhydride C■) with α-aminonitrile (IX) in an inert solvent, removing the solvent, and heating with an acetic anhydride solvent in the presence of catalytic amounts of sodium acetate and potassium acetate. Compound α) is obtained.

Then, by treatment with a strong acid such as sulfuric acid, if necessary in a halogenated hydrocarbon solvent such as chloroform, methylene chloride, carbon tetrachloride, etc., a compound]) (W=O) is obtained. Compound (II) (R=o) thus obtained is treated with an alkoxy anion corresponding to R in an alcoholic solvent corresponding to H
i(g) is obtained.

Reaction formula 5 % formula % (In the formula, w, x, y, R, R:, R8 and R1 represent the same meaning as above.) In other words, compound source) or CX[[[) is replaced with an inert aproton. The reaction is carried out using a neutral solvent such as tetrahydrofuran, an alcohol ROH corresponding to 9 different H groups in the dioxane ring, at a reaction temperature of about 20°C to 50°C, and if necessary, adding an organic base such as sodium hydride or triethylamine as a catalyst. By doing so, the compound CI) of the present invention can be obtained.

The raw material compound (and width) can be synthesized according to the synthetic route of [Method O] below.

(In the formula, W, X, Y, R, R', R''>j and R3 have the same meanings as above.) Dicyclohexylcarbodiimide (Dec), If necessary, a dehydration condensation agent such as acetic anhydride or trifluoroacetic anhydride is reacted in a halogenated hydrocarbon or ether type (e.g. tetrahydrofuran) solvent, or the compound ar) hydrogen, toluene,
In an aromatic hydrocarbon solvent such as xylene, an alkali metal hydride such as sodium hydride, 1,8-diazabicyclo[5
.

Intermediate compound (n) (II
(IV) [Friend, (X-OH,, y=o, R
'=OH'') except < ], CV) Cfc,
(Excluding (X=OH,, y=o, R''=aa, )<']
, (M)Gl)α) (XI) (XII) CMM)
is a new compound.

This will be specifically explained using the following synthesis example.

Synthesis Example 1 1-Amino-1-buten-3-one 10.0f (0,1
18 mol), ethyl ethoxymethylene ogizaroacetate 2a,0r (0,1f 5 mol) in diethyl ether 5
The mixture was dissolved in water and stirred at room temperature for 12 hours. A saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with diethyl ether.

After washing with water and drying, the solvent was distilled off to obtain a crude product of the title compound, which was purified by distillation under reduced pressure to obtain the title compound 14. Of (0,054 mol) yield 47N was obtained.

[Pale yellow liquid, boiling point 160-183℃ (0.3mmHr)
), refractive index mv t s 17o , pnR(δ(1
(aDc4)): 1.41 (t, J=6.5Hz
, 3H), 1.58(t, J=6.5H2,3H
) 2.17 (s, 5FL), 4.40 (q,
J=6.5Hz, 2H), 4.51(q.

J=/s, 5Hz, 2H), 8.67(d, J=
2Hz, IH), 9.23((1°J=2Hz,
IH) ] Synthesis Example 2 1-phenyl-3-amino-2-propen-1-one 1
4.7 f (0.10 mol), ethyl ethoxymethylene ogizaloacetate 22. Of (0,098 mol) was dissolved in tetrahydrofuran.

After stirring at room temperature for 5 hours, heat to reflux temperature.

The reaction was further continued for 1 hour. After distilling off the solvent under reduced pressure, a saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, extracted with diethyl ether, the organic layer was washed with water, and the solvent was distilled off after drying to obtain the crude product of the title compound. , which was purified by column chromatography to obtain the title compound 24.
Of (0,074 mol) yield 75N was obtained.

[Pale yellow crystal, PMR (δ value (ODO4)): 1
．． 37 (t.

J=6.5Hz, 3H), 1.41 (t, :J
=6.5Hz, 5H), 4.38(q, J=6.
5H2,2H), 4.45((1,;f=6.5Hz
, 2H).

7.30-8.10 (m, 5H), 8.48 (+1.
, T+=2Hz, IH).

&96(d, J=2Hz, IH) ] Synthesis Example Pyridinecarboxylic acid diethyl ester synthesized in Synthesis Example 1 6.0f (0,025 mol) in methanol 100I1
0.5F of sodium borohydride was added to a solution of 1 and stirred at room temperature for 3 hours. Dilute hydrochloric acid was added to the reaction solution of 9, and the mixture was extracted with diethyl ether.

The organic layer was washed with water, and the solvent was distilled off after drying to give a crude alcohol product of 5.4 F (0,020 mol), yield 88.
I got N. Crude alcohol 5.42 (0,020 mol), para-toluenesulfonic acid 0.1, ? , xylene 5
The mixture was reacted at reflux temperature for 24 hours while water was separated using a moisture meter.

After cooling, the solvent was distilled off under reduced pressure, water was added, and extraction was performed with chloroform. The organic layer was washed with water, dried, and the solvent was distilled off to obtain a crude product of the title compound, which was purified by column chromatography. The title compound was 1.85 F (0
, 074 mol) yield λ 37% was obtained. [Oil, refractive index bowl'; 1.5106
゜PMR (δ value (0,001s)): 1-40
(t, J=6Hz, 5H).

1.38 (t, J=6Hz, !IH), 4.42
((1, J=6H2,21°4.38(q, J=6H
z, 2H), 5.50(d, , T=11Hz,
IE[).

5.74 ((1,, T=17H2, IH), 6.7
7 (d, d, J=11Hz.

17Hz, IH), &12(d, J=2Hz, iH),
13.70 (d, J = 2Hz, IH)] Synthesis Example 4 Hydrogen in a 100 methanol solution of 5-acetyl-6-methylpyridine-2,3-dicarboxylic acid diethyl ester IQ, Of (0,036 mol) Sodium boronate 0.
After adding 72 and stirring at room temperature for 3 hours, the reaction solution 9 was made acidic with diluted hydrochloric acid and extracted with diethyl ether. After drying the organic layer, the solvent was distilled off to obtain the dialcohol crude product 9.6.
1 (0,054 mol) yield 95X was obtained. [PMR(δ
Direct (ODO4): 1.35 (t, J=6Hz
, 3E(), 1.33(t, J=61(Z, 3H)
, 1.44 (d, J=6Hz, 3H), 2-55 (a,
5H), 2.93 (b8. 1H), 4.32 ((1,
J=6Hz, 2H).

4.38((1, J=6Hz, 2EI), 5.09((
1, J=6Hz, IH).

13.27 (8.1g) Alcohol crude product & Of (0,028 mol).

Para-toluenesulfone (IRo, st, xylene 100) was reacted all day and night at reflux temperature while separating water using a water separator. After cooling, the solvent was distilled off under reduced pressure.

Water was added and extracted with chloroform. After washing the organic layer with water and drying, the solvent was distilled off to obtain a crude product of the title compound. This was purified by column chromatography to obtain the title compound 4.3F (
0,0163 mol) yield 'rL,.

I got 58X. [Oil, refractive index layer D1.5324°P
MR (δ1 direct (ODC4)): 1.40 (t, J=
6Hz, 3H).

1.39 (t, J=6H2,3H), 2.62 (s
, 3H), 4.39(q, , T=6Hz, 2H
), 4.43 (q, J-6Hz, 2H), 5.
53 (d, J=10H2, IH), 5.75 (d,
J=17Hz, 1H), 6.86 (d, d.

J=10Hz, 17Hz, iH), 8.15(s
, IH) Synthesis Example 1-Amino-4-methyl-1-penten-3-one 3.
a y (0.03 mol) and ethyl ethoxymethylene oxyaloacetate Otsu 3P (0.03 mol) were dissolved in 50 mol of ethanol and stirred at room temperature for 12 hours. The solvent was distilled off under reduced pressure, a saturated aqueous sodium bicarbonate solution was added, the oil was extracted with diethyl ether, washed with water, and the solvent was distilled off to obtain a crude product of the title compound, which was purified by column chromatography. Title compound 1.69 (4,4
A yield of 15X (mmol) was obtained.

[Oil, PMR (δ value (ODO4)): 1.24
(d, J = 6.5Hz, 6H), 1j8(t,
J=6.5Hz, 3H), 1.41(t.

, T=6.5Hz, 3H), 3.52(7th,
:r=6.5Hz, IH).

4.40 (q, J=6.5H2,2H), 4.4
7 (q, J-6, 5Hz, 2H).

8.13 (d, J=2Hz, IH), 9.18 (
d, J=2H2,1H)] Synthesis Example 6 Pyridinedicarboxylic acid diester 5 synthesized in Synthesis Example 1
．． 0f (0,0189 mol) in methanol 30g, water 5g
0 go, sodium hydroxide 2.0? (0,045 mol) and stirred at room temperature for 12 hours. Next, after neutralizing with hydrochloric acid, the solvent was completely distilled off under reduced pressure, and 20% of ethanol was added.
0g was added and filtered, and the F liquid fc0R filter solvent was distilled off to obtain 3.6 f (0,0172 mol) of the title compound.
A yield of 91X was obtained. [White crystals, melting point 127-138℃
(decomposition), PMR (δ direct (DMSO-(1,)): 2
．． 70 (e.

3H), 7.90-9.05 (BS, 2H),
8.68 ((1, J=2Hz, IH).

9.24 (tl, J=2Hz, IH) ] Synthesis Example Pyridinedicarboxylic acid diester 1 synthesized in Synthesis Example 2
Add 2.55' (0,038 mol) to a mixed solution of 90 g of methanol, 90 g of water, and 6.02 g of sodium hydroxide,
After refluxing the mixture for 2.5 hours, the solvent was distilled off under reduced pressure, and the resulting residue was dissolved in water and acidified with concentrated hydrochloric acid to precipitate white crystals. The white crystals were separated from each other and dried to give the title dicarboxylic acid a, 4F (0,031 mol), yield 8.
I got 2N.

[Pale yellow crystal, PMR (δ value (DMSO-d6),)
: 7.20-8.00 (m, 5H), 8.53 (
d, I=2H2,1H), 9.04(a.

J=2Hz, LH), 10.50~11.30(b
s, 2H)] Synthesis Example Pyridinedicarboxylic acid 2.1F (0
, 01 mol) and 9100 d of anhydrous vinegar at 90 to 100°C.
Heat and stir for an hour. After the reaction was completed, the solvent was distilled off under reduced pressure to obtain the title compound t a y (9.4 mmol). [Gray-white crystals, PMR (δ value (aDc4)): 17 y
(e, s a), &61(a, :r x2Hz
.

IH), 9.00(d,:J=2H2,1H) ] Synthesis Example 9 O 5-acyl-6-methylpyridine-43-dicarboxylic acid diethyl ester 5.5 F, Vinegar rR 5 ml.

32X hydrobromic acid aqueous solution g3.2f was cooled to 0°C.

4. viridisonohydropromide barbromide dissolved in acetic acid 50-. Of was added dropwise, and the temperature was gradually raised from 0°C to room temperature. Water was added to the reaction solution, and the mixture was extracted with diethyl ether. Wash the organic layer with water.

After drying, the solvent was distilled off to obtain the title compound 3,85.
f (purity 8ON) was obtained. [Oil, refractive index 4oz, PMR (δ direct (ancz, ))
'1.37 (t, J=6.5Hz, 3H),
1. ! 15 (t, J=6.5Hz, 5H).

2.72 (s, 3H), 4.31 (s, 2H)
, 4.31 (q, :r=6.5Hz.

2K), 4.36(q, I=6.5Hz, 2H),
8.26 (s, IH)] From Synthesis Example 1, IC was performed in the same manner as the synthesis side control, Table 1.

Compounds GV), (V) and (W) shown in Tables 2 and 3 were synthesized.

Table 1 In the table, 9Mθ represents a methyl group, and Ph represents a phenyl group.

In Table 2, Me represents a methyl group and Ph represents a phenyl group.

In the table, Me represents a methyl group and ph represents a phenyl group.

Next, the compound of the present invention represented by the general formula CI) is the above-mentioned (
It can be synthesized by any method of Reaction Formula 1), (Reaction Formula 2) or (Reaction Formula 3).

Specific examples thereof are listed in Table 4. however.

The compounds of the present invention are not limited to these.

In Table 4, Me is a methyl group, Kt is an ethyl group,
Ph represents a phenyl group.

The compounds of the present invention in Table 4 are the following synthesis examples.

Reference is made for formulation examples and test sequences.

Next, the nine compounds of the present invention will be explained by giving some specific synthesis examples. However, it is not limited to these only.

Synthesis Example 9 Diethyl pyridine/dicarboxylate synthesized in Synthesis Example 4 3.
By hydrolyzing Of (12 mmol) in the same manner as in Synthesis Example 6, 2.52 of 5-ethynylpyridine-5-dicarboxylic acid was obtained.

20 grams of acetic anhydride was added thereto, and the mixture was heated and stirred at 90 to 100°C for 5 hours. The solvent was distilled off under reduced pressure to obtain compound (Vi) (X
A crude product of =H, Y=OH* R″=a was obtained. This crude product was treated with 2-amino-2,3-dimethylbutanamide ((i) (w = o, R1= ]H, , r = C
The mixture was stirred vigorously at room temperature all day and night.

The solvent was distilled off under reduced pressure to obtain compound (n) (w=o, x=
H, Y=O horse, R= H, al=aq,, R1=
A crude product of au(aH,),') was obtained. Add 25 g of water to this crude product.

1.41 liters of sodium hydroxide was added, and stirring was continued for 3 hours at a temperature of 80°C. After cooling, the solution was acidified with concentrated hydrochloric acid, extracted with chloroform, the organic layer was washed with water, dried, and the solvent was distilled off to obtain a crude product of the title compound. This was further purified by column chromatography to obtain 1.32 white crystals of the compound A1 of the present invention.

Synthesis Example 10 (Compound of the Invention &2) Compound (Vi) (X=H, Y=C!H,, R'=CH,
) 2.0? , 2-amino-2,3-dimethylbutanamide N) (W= O, R'= OH,, R'= 0H
(OH, ), ) 1.5 f and 50 rnt of pyridine were vigorously stirred at room temperature all day and night.

The solvent was distilled off under reduced pressure F, and the compound ([[) (iv=a, x
=H, Y=O turtle, R=H, R'=OH,, R"= 0H
(OH,),.

A crude product of R'=CH,) was obtained. This crude product is mixed with 2 parts of water.
5d, add 1.42 ml of sodium hydroxide and heat at 80°C.
Stirring was continued for an hour. After cooling, insoluble materials were removed and hydrochloric acid water was added to make the mixture acidic. The organic layer was extracted with ethyl acetate, washed with water, dried, and the solvent was distilled off to obtain a crude product of the title compound.

This was further purified by column chromatography to obtain 1.12 white crystals of compound 462 of the present invention.

Synthesis example 11 (Invention Compound Demon 3) Compound CM synthesized on the synthesis example day) (x=cH,.

Y=Q, R"F()7.1F, 2-amino-43-dimethylbutanamide C) (w=o, a'-a horse R
1= O, [((OH,),) 5.4 f , 4
- 20 grams of picoline was vigorously stirred at room temperature all day and night. The solvent was distilled off under reduced pressure to form the compound ((r)(w=o, X=CH
,, Y=O, R=H.

R"-OH,, R"-C! H(OH,), , R'
A crude product of =H) was obtained. To this crude product were added 25 d of water and 6.11 ml of sodium hydroxide, and the mixture was stirred at a temperature of 80° C. for 6 hours.

After cooling, all insoluble matter was removed by filtration, and hydrochloric acid water was added to make it acidic. Extract with chloroform and wash the organic layer with water.

After drying, the solvent was distilled off to obtain a crude product of the title compound. Furthermore, this was dI by column chromatography.
I obtained 4.01 white crystals of the compound of the present invention with a point of 3.

1 Upper L ○ (Compound of the present invention 7) Compound (I)C Compound of the present invention 44) 2. Of, acetic acid 20
rnt bromine2. Of was slowly added dropwise. After stirring at room temperature for 5 hours, the solvent was distilled off under reduced pressure, and the mixture was extracted with chloroform. The organic layer was washed with water, dried, and the solvent was distilled off to obtain the title compound.

Compound (T) (Compound A4 of the present invention)1. ay, ethyl calperh'-to 0.67f ethyl alcohol 2゜go 3
Time passed away. After cooling, the solvent was distilled off under reduced pressure, and the remaining residue was dissolved in tetrahydrofuran. All insoluble matter is removed by filtration, and F? 'l[ was concentrated under reduced pressure. When isopropyl ether was added to the residue, white crystals were precipitated. The crystals were distributed from house to house and dried to obtain white crystals 0.72 f of Invention Hardware Shop 9.

Compounds of the present invention C shown in Table 5 can be prepared using the reaction of h shift 7>- in Reaction formula 1), (Reaction formula 2) or (Reaction formula 3).
I) can be synthesized.

Table 5-55 When using the compounds of the present invention as herbicides or plant growth regulators, suitable carriers are generally used, such as clay, talc, and bentonite.

Solid carriers such as diatoms or water, alcohols (methanol, ethanol, etc.), aromatic hydrocarbons (benzene,
It can be used in combination with liquid carriers such as toluene, xylene, etc.), tetrahydrocarbons, ethers, ketones, esters (ethyl acetate, etc.), acid amides (dimethylformamide, etc.), and can be applied as desired. emulsifier 2 dispersant,
By adding suspending agents, penetrating agents, spreading agents, stabilizers, etc., liquid formulations,
It can be put to practical use in any desired dosage form such as emulsion, wettable powder, powder, zero granule, and flowable preparation. The content of the active ingredient compound in these preparations is not particularly limited, but is generally desirably in the range of 1.0 to 90.0 weight tx.

If necessary, it may be mixed with other herbicides, various insecticides, fungicides, plant growth regulators, synergists, etc. at the time of formulation or spraying. Types of herbicides to be mixed: 1
For example, farm.

Shizuku 56 F'ari Chemicals, Handbook (F'ari Chemical
als HPhrxl-book), 70th edition (198
Examples include the compounds described in 4).

Note that the compound of the present invention can be applied to control various weeds in agricultural and horticultural fields such as fields, paddy fields, and orchards, as well as in non-agricultural areas such as agricultural fields, vacant lots, and railway edges. There are differences depending on the application situation, application period, application method, target vehicle type, cultivated crops, etc., but in general, the appropriate amount of active ingredient is about 0.000 to 10.00 per hectare.

Next, examples of formulations of herbicides and plant growth regulators containing the compound of the present invention as an active ingredient will be shown, but the invention is not limited thereto. In addition, in the following formulation examples, "parts" mean parts by weight.

Formulation Example 1 Wettable powder The above ingredients are uniformly mixed and pulverized to make an irrigant. When using, the above-mentioned hydrating agent should be diluted 50 to 10,000 times so that the amount of active ingredient is about 1 hectare.

Spray it to a level of 0.5 to iokg.

Formulation Example 2 Emulsion mixture: Toho Chemical Industry (Kiku brand name) The above is mixed uniformly to form an emulsion. When used, the above emulsion is diluted 50 to 1.000 times and sprayed at an amount of active ingredient of 0.005 kF to 10 kF per hectare.

Formulation Example 5 Granules and above 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. For stool use, use the above granules in the amount of active ingredient or per hectare.
Spray so that the amount is between 100 and 100 yen.

Formulation example 4 Flowable agent Tsurupol 3353. Lunox 1oooa and 1X
The xanthan gum aqueous solution is uniformly dissolved in water, and then the compound 41 of the present invention is added and stirred well, followed by wet grinding in a sand mill to obtain a flowable agent. When using the above flowable agent? It is diluted 50 to 1,000 times and sprayed so that the amount of active ingredient is 10 to 10 kg per hectare.

Formulation example 5 Hydrating agent The above is uniformly mixed and pulverized to form a wettable powder.

Next, the herbicidal effects of the compounds of the present invention will be specifically explained by giving test examples.

Test Example-1 Weeding effect test by soil treatment Vertical 301. horizontal 2
21. Put sterilized diluvial soil in a glass-backed box with a depth of 61 cm, and grow rice, wildflowers, cyperus, japonica,
Dogfish.

Corn, wheat, soybean, cotton, and 1-kilobarium annuus were sown, and after covering the soil with approximately 1.5 strips of soil, the amount of the active ingredient was uniformly spread over the soil surface at a predetermined ratio. The medicinal solution used for spraying was the irrigation agent, emulsion or flowable agent 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.

Judgment Criteria 5: Weed killing rate 90X or higher (almost complete death) 4...
・Weed killing rate 70-9 ON 5...Weed killing rate 40-70 The above weed killing rate was determined by the formula F by measuring the weight of above-ground plants in the chemical-treated area and the weight of above-ground plants in the untreated area.
It is something.

In addition, phytotoxicity to various crops was investigated according to the following criteria. The results are shown in Table 6.

Criterion 5: The crop is almost completely dead 4: The phytotoxicity to the crop is significant 3: The phytotoxicity to the crop is observed 2°°°The phytotoxicity to the crop is slightly - 1°° The phytotoxicity to the crop is Hardly observed 0゛°°No chemical damage to crops Test Example-2 Herbicidal effect test results by spasmodic leaf treatment 30I
M, horizontal 221. Sterilized diluvial soil was placed in a plastic box with a depth of 61 cm, and rice, wildflowers, cyperus, cyperus, and grass were planted.

Leafminer, corn, wheat, soybean.

Cotton and beet seeds were sown in spots and covered with approximately 1.5 tx of soil. When various plants reach the 2-3 leaf stage, make sure to spray the active ingredient evenly on the stems and leaves so that the amount of active ingredients is in the prescribed ratio.

The chemical solution for spraying (d) The hydrating powder, emulsion, or flowable agent of the above formulation example was diluted with water and sprayed with a small sprayer over the entire foliage of various weeds and crops. 4 weeks after spraying the chemical solution, it was applied to various weeds. Herbicidal effects and phytotoxicity against each rice crop were investigated according to the criteria of Test Example-1.

The results are shown in Table 7.

Table 6 Comparative compound (A) in Table 6 [- posthumous name: linuron (L
The structural formula of the reference compound (B) [generic name: acifluorfen (, AOlfllX) and Sodium] is shown in Table 7.
] is the structural formula.

-Trial @@J25- Applicability test for soybean cultivation bed (collection treatment) Diameter 30 tyn, depth 12. Fill the shoulder plastic pots with sterilized diluvial soil and grow soybeans, johnsongrass,
Japanese barnyard grass, foxtail grass, and white grass.

Seeds of Onamia japonica, Datura morning glory, Malva morning glory, Ichibi, Golden deer, Inubu, and Hornet were sown, and about 1.5 liters of soil was covered. In addition, plant the clumps of Japanese commonweed in separate pots at a depth of 1.5 m. When the various crops reached the first leaf stage, the active ingredients were uniformly sprayed onto the collecting area at a predetermined ratio.

The chemical solution used for spraying was the hydrating agent of the formulation example described above diluted with water and sprayed using a small sprayer over the entire surface of the collection areas of various plants. Four weeks after spraying the chemical solution, the effect on various plants was investigated according to the criteria of Test Example 1 above.

The results are shown in Table 8.

Table 8

Claims (3)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, W represents an oxygen atom or a sulfur atom. X is
Hydrogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
4 lower alkoxymethyl group, lower alkylthiomethyl group having 1 to 4 carbon atoms, lower haloalkyl group having 1 to 4 carbon atoms, lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, benzyl group or optionally substituted phenyl group or pyridyl group (this substituent includes a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group). . Y is an oxygen atom, a sulfur atom, a monosubstituted nitrogen atom {this substituent includes a lower alkyl group having 1 to 4 carbon atoms, a carbon number 1
to 4 lower alkoxy groups, lower alkoxycarbonylamino groups having 1 to 4 carbon atoms, or optionally substituted phenyl groups or pyridyl groups (such substituents include lower alkyl groups having 1 to 4 carbon atoms, lower alkyl groups having 1 to 4 carbon atoms, -4 lower alkoxy group, halogen atom, nitro group, cyano group or trifluoromethyl group). }, or a di-substituted carbon atom {this di-substituent is each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 3 to 6 carbon atoms; Cycloalkyl group or optionally substituted phenyl group or pyridyl group (substituents include lower alkyl group having 1 to 4 carbon atoms, lower alkoxy group having 1 to 4 carbon atoms, halogen atom, nitro group, cyano group) or a trifluoromethyl group.) In addition, the di-substituents can be combined to form a ring, and the di-substituents can be substituted with a lower alkyl group having 3 to 6 carbon atoms, which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. Indicates a cycloalkyl group. } represents. R is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such as a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, or a lower alkyl group having 3 carbon atoms) -6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, tri-lower alkyl ammonium group, or optionally a halogen atom, lower alkyl having 1 to 4 carbon atoms group, carbon number 1-4
represents a phenyl group which may be substituted with a lower alkoxy group or a nitro group. ), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (this substituent includes a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, 2 lower alkoxy groups having 1 to 3 carbon atoms), or phenyl group), lower alkynyl group having 2 to 5 carbon atoms, oxacycloalkyl group having 5 to 6 carbon atoms, and 2 to 6 carbon atoms.
-5 mono-, di-, or trihaloalkenyl group, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group, alkylthioalkyl group, cycloalkyl having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms represents a group or a cation selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R^1 represents a lower alkyl group having 1 to 4 carbon atoms. R^2 represents a lower alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Furthermore, R^1 and R^2 represent a cycloalkyl group having 3 to 6 carbon atoms which can be combined to form a ring and which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. . R^2 is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a 1 to 4 carbon atom;
-4 alkylthio group, phenoxy group, haloalkyl group having 1 to 4 carbon atoms, haloalkoxy group having 1 to 4 carbon atoms, or alkylsulfonyl group having 1 to 4 carbon atoms. ] or an optical isomer of the derivative (
However, if R^1 and R^2 are not the same). (2) General formula (II): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) [In the formula, W represents an oxygen atom or a sulfur atom. X is
Hydrogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
4 lower alkoxymethyl group, lower alkylthiomethyl group having 1 to 4 carbon atoms, lower haloalkyl group having 1 to 4 carbon atoms, lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, benzyl group or optionally substituted phenyl group or pyridyl group (this substituent includes a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group). . Y is an oxygen atom, a sulfur atom, a monosubstituted nitrogen atom {this substituent includes a lower alkyl group having 1 to 4 carbon atoms, a carbon number 1
to 4 lower alkoxy groups, lower alkoxycarbonylamino groups having 1 to 4 carbon atoms, or optionally substituted phenyl groups or pyridyl groups (such substituents include lower alkyl groups having 1 to 4 carbon atoms, lower alkyl groups having 1 to 4 carbon atoms, -4 lower alkoxy group, halogen atom, nitro group, cyano group or trifluoromethyl group). }, or a di-substituted carbon atom {this di-substituent is each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, or a lower haloalkyl group having 3 to 6 carbon atoms cycloalkyl group or optionally substituted phenyl group or pyridyl group (this substituent has 1 to 4 carbon atoms)
lower alkyl group, lower alkoxy group having 1 to 4 carbon atoms,
Indicates a halogen atom, nitro group, cyano group or trifluoromethyl group. ) Furthermore, the di-substituents can be combined to form a ring, and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted by a lower alkyl group having 1 to 3 carbon atoms. } represents. R is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such as a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, or a lower alkyl group having 3 carbon atoms) -6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, tri-lower alkyl ammonium group, or optionally a halogen atom, lower alkyl having 1 to 4 carbon atoms group, carbon number 1-4
represents a phenyl group which may be substituted with a lower alkoxy group or a nitro group. ), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (this substituent includes a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, 2 lower alkoxy groups having 1 to 3 carbon atoms), or phenyl group), lower alkynyl group having 2 to 5 carbon atoms, oxacycloalkyl group having 5 to 6 carbon atoms, and 2 to 6 carbon atoms.
-5 mono-, di-, or trihaloalkenyl group, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group, alkylthioalkyl group, cycloalkyl having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms represents a group or a cation selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R^
1 represents a lower alkyl group having 1 to 4 carbon atoms. R^2 represents a lower alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Moreover, R^1 and R^2 can be taken together to form a ring, and represent a cycloalkyl group having 3 to 6 carbon atoms which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. R^3 is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a 1 to 4 carbon atom;
-4 alkylthio group, phenoxy group, haloalkyl group having 1 to 4 carbon atoms, haloalkoxy group having 1 to 4 carbon atoms, or alkylsulfonyl group having 1 to 4 carbon atoms. ] or an optical isomer of the derivative (
However, if R^1 and R^2 are not the same. ) with an aqueous solution of alkali metal hydroxide or alkaline earth metal hydroxide, the presence of phosphorus oxychloride, phosphorus pentachloride, alkali metal hydride or alkaline earth metal hydride in an inert solvent. or cyclization using a dehydrating reagent such as dicyclohexylcarbodiimide; or, in some cases, esterifying the above cyclized product with an alkylating agent such as diazomethane, dialkyl sulfate, or Meyerbain reagent. , or general formula (I) characterized by esterification or transesterification with alcohol ROH corresponding to R: ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) (In the formula, W, X, Y, R , R^1, R^2 and R^3
has the same meaning as above. ) or an optical isomer of the derivative (however, R^1 and R^2
are not the same). (3) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) [In the formula, W represents an oxygen atom or a sulfur atom. X is
Hydrogen atom, lower alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
4 lower alkoxymethyl group, lower alkylthiomethyl group having 1 to 4 carbon atoms, lower haloalkyl group having 1 to 4 carbon atoms, lower alkylsulfonylmethyl group having 1 to 4 carbon atoms, benzyl group or optionally substituted phenyl group or pyridyl group (this substituent includes a lower alkyl group having 1 to 4 carbon atoms, a lower alkoxy group having 1 to 4 carbon atoms, a halogen atom, a nitro group, a cyano group, or a trifluoromethyl group). . Y is an oxygen atom, a sulfur atom, a monosubstituted nitrogen atom {this substituent includes a lower alkyl group having 1 to 4 carbon atoms, a carbon number 1
to 4 lower alkoxy groups, lower alkoxycarbonylamino groups having 1 to 4 carbon atoms, or optionally substituted phenyl groups or pyridyl groups (such substituents include lower alkyl groups having 1 to 4 carbon atoms, lower alkyl groups having 1 to 4 carbon atoms, -4 lower alkoxy group, halogen atom, nitro group, cyano group or trifluoromethyl group). }, or a di-substituted carbon atom {this di-substituent is each independently a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 1 to 4 carbon atoms, a lower haloalkyl group having 3 to 6 carbon atoms; Cycloalkyl group or optionally substituted phenyl group or pyridyl group (substituents include lower alkyl group having 1 to 4 carbon atoms, lower alkoxy group having 1 to 4 carbon atoms, halogen atom, nitro group, cyano group) or a trifluoromethyl group.) In addition, the di-substituents can be combined to form a ring, and the di-substituents can be substituted with a lower alkyl group having 3 to 6 carbon atoms, which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. Indicates a cycloalkyl group. } represents. R is a hydrogen atom, a di-lower alkylimino group, an optionally substituted lower alkyl group having 1 to 5 carbon atoms (such as a lower alkoxy group having 1 to 3 carbon atoms, a hydroxy group, or a lower alkyl group having 3 carbon atoms) -6 halocycloalkyl group, carboxyl group, lower alkoxycarbonyl group, cyano group, dialkylphosphonyl group, halogen atom, benzyloxy group, tri-lower alkyl ammonium group, or optionally a halogen atom, lower alkyl having 1 to 4 carbon atoms group, carbon number 1-4
represents a phenyl group which may be substituted with a lower alkoxy group or a nitro group. ), an optionally substituted lower alkenyl group having 2 to 5 carbon atoms (this substituent includes a lower alkoxy group having 1 to 3 carbon atoms, a lower alkoxycarbonyl group, 2 lower alkoxy groups having 1 to 3 carbon atoms), or phenyl group), lower alkynyl group having 2 to 5 carbon atoms, oxacycloalkyl group having 5 to 6 carbon atoms, and 2 to 6 carbon atoms.
-5 mono-, di-, or trihaloalkenyl group, haloalkynyl group having 2 to 5 carbon atoms, glycidyl group, alkylthioalkyl group, cycloalkyl having 3 to 6 carbon atoms which may be substituted with an alkyl group having 1 to 3 carbon atoms represents a group or a cation selected from alkali metal atoms, alkaline earth metal atoms, ammonium or organic ammonium. R^
1 represents a lower alkyl group having 1 to 4 carbon atoms. R^2 represents a lower alkyl group having 1 to 4 carbon atoms or a cycloalkyl group having 3 to 6 carbon atoms. Furthermore, R^1 and R^2 represent a cycloalkyl group having 3 to 6 carbon atoms which can be combined to form a ring and which may be substituted with a lower alkyl group having 1 to 3 carbon atoms. . R^3 is a hydrogen atom, a halogen atom, a lower alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a carbon number 1
-4 alkylthio group, phenoxy group, haloalkyl group having 1 to 4 carbon atoms, haloalkoxy group having 1 to 4 carbon atoms, or alkylsulfonyl group having 1 to 4 carbon atoms. ] or an optical isomer of the derivative (
(provided that R^1 and R^3 are not the same) A herbicide characterized by containing one or more of the following as an active ingredient.