JPH0733748A - Pyrimidine derivative and herbicide - Google Patents

Abstract

PURPOSE:To obtain a novel pyrimidine derivative which is useful as a selective herbicide for plowed land, paddy field and untilled lands because it show selectivity to important crop plants and excellent herbicidal effect on a variety of weeds with reduced doses. CONSTITUTION:A compound of the formula I [Ra is H, halogen, 1 to 6C alkoxy, 1 to 6C (halo)alkyl; Rb is phenyl, benzyl pyridyl, thienyl, funyl all of which may be arbitrarily substituted with substituents such as 1 to 4C alkyl, halogen or the like; Z is N, CH; Rc is SR<1>, OR<2>, N(R<3>)R<4> (R<1> to R<4> are H, 1 to 6C alkyl, 1 to 6C alkenyl, 1 to 6C alkinyl where R<3> and R<4> may form a 3 to 7-membered ring together with bound N atom and the ring may include O, N, S atoms)], for example, 5-[2-(4-fluorophethyl)-6-methylthio-4-pyrimidyl]-4-triflurormethyl- pyrimidine. The compound of the formula I in which Rc is SR<1> and Z is N, namely the compound of formula IV, is obtained by subjecting a 5- acylpyrimidine derivative of formula II as a starting substance to the reaction path way given in the Figure.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel pyrimidine derivative and a selective herbicide containing the derivative as an active ingredient.

[0002]

2. Description of the Related Art Conventionally, many herbicides have been put into practical use in order to protect important crops such as rice, soybean, wheat, corn, cotton and beet from weeds and to improve the productivity of these important crops. . These agents can be broadly classified into three categories, upland action, paddy field, and non-arable land, depending on the application scene. Furthermore, in each case, it can be classified into a soil admixture treatment type, a pre-emergence soil treatment type, a post-emergence treatment (stem and leaf treatment) type and the like depending on the application method of the drug.

It is clear that productivity of important crops affects the food economy of each country as the population of the world increases in recent years. With these changes, it is inevitable that the traditional agricultural form will change toward the 21st century. Actually, there is an increasing need for farmers to develop herbicides that can kill or control economically and efficiently weeds that interfere with crop cultivation.

As such a herbicide, the development of a drug having the following conditions has been earnestly desired. Those that have a high herbicidal effect at low doses (especially it is necessary to kill weeds by spraying as low a dose as possible from the viewpoint of environmental protection), those that have an appropriate residual effect (in recent years, soil residue It has been a problem that long drugs damage the succeeding crops, and it is important to show appropriate residual effect after spraying.) Those that kill weeds immediately after spraying (after chemical treatment) , The next crop can be sown and transplanted in a short period of time.) The number of times of chemical treatment is small (it is important for farmers to minimize the number of complicated weed control work).

A wide range of weed control objects (for broad-leaved weeds, gramineous weeds, perennial weeds, and other weed species with different properties, it is desirable to use a single drug to control these weeds) and an application method. A large amount (a stronger herbicidal effect can be obtained by combining the effects of soil treatment and foliage treatment), and one that does not show phytotoxicity that poses a problem for crops (for arable land where crops and weeds are mixed) Among them, those capable of selectively killing only weeds are preferable.) However, existing herbicides do not meet all of these requirements.

[0006]

In view of such a situation, the present inventors show selectivity for important crops and have excellent herbicidal effect against many weeds with a low dose. As a result of continuing research to develop a herbicide having both soil treatment and foliar treatment, the formula (I):

[0007]

[Chemical 2]

[In the formula, Ra represents a hydrogen atom, a halogen atom,
_{Represents a} C _1-6 alkoxy group, a C _1-6 alkyl group or a C _1-6 haloalkyl group, and Rb represents a phenyl group, a benzyl group, a pyridyl group, a thienyl group or a furyl group which may be optionally substituted with a substituent. (However, the substituent is C _1-4
It represents one or more selected from an alkyl group, a halogen atom, a C _1-4 haloalkyl group and a C _1-4 haloalkoxy group. ), Z represents a nitrogen atom or CH, and R
c represents SR ¹ , OR ² or N (R ³ ) R ⁴ (provided that R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, a C _1-6 alkyl group, a C _1-6 alkenyl). Group or C
_1-6 alkynyl group is represented, and R ³ and R ⁴ may form a ring of 3 to 7 together with the nitrogen atom to which they are bound, and the ring may contain an oxygen atom, a nitrogen atom or a sulfur atom. . ) And a pyrimidine derivative represented by the formula (hereinafter referred to as the compound of the present invention).

The compound of the present invention is used as a herbicide for upland fields, paddy fields and non-cultivated lands, regardless of the method of soil treatment or foliage treatment.
American stag deer, Malva morning glory, Inuyuyu, Aobiyu, Onami fir, Ragweed, Sunflower, Toothbrush,
Thistle, thistle, syringa, himejeon, pupa, nuptera, thorns, staghorn, buckwheat,
Broad-leaved leaves such as purslane, white-tailed, koa-kaza, broom, chickweed, red-necked corn, communis serrata, serrata, Astragalus serrata, periwinkle, red-crowned corn, yaemgra, madder, violet, horned grass, ebisugusa, kosendangusa, etc.

Wild sorghum, giant millet, Johnsongrass, barnyard grass, blackgrass, crabgrass, oats, cedar, Enocologsa, grass weeds such as Prunus aegypti, Cyperaceae weeds such as Haesumegae, Heraomoduka, Periwinkle, Periwinkle, Periwinkle, Periwinkle, Periwinkle, Periwinkle. It has a high herbicidal activity with low dosage in various paddy field weeds such as kurogwai, azalea, konagi, hirshiro, white squirrel, and squirrel.

The compounds of the present invention can be synthesized, for example, by the methods shown in Schemes 1 to 8 (Ra and R in Schemes 1 to 8).
b, Rc, Z, R ¹ , R ² , R ³ and R ⁴ have the same meanings as described above, R ¹¹ represents a C _1-4 alkyl group, and Ha
l represents a halogen atom, n represents 1 or 2, and M represents a sodium atom or a potassium atom. ).

[0012]

[Chemical 3]

(1) In Scheme 1, as the first step, 5-acylpyrimidine derivative (II) is reacted with carbon disulfide and an alkyl halide in the presence of a base to give a ketene dithioacetal derivative (III), and the second step As a compound (IV) of the present invention by reacting (III) with an amidine derivative in the presence of a base.
It represents a method of manufacturing (when Rc = SR ¹ and Z = N).

[0014]

[Chemical 4]

(2) Scheme 2 represents a method for producing the compound (V) of the present invention (when Rc = OR ² and Z = N) by reacting (III) with an amidine derivative in the presence of a metal alkoxide.

[0016]

[Chemical 5]

(3) In Scheme 3, (IV) is reacted with metal alkoxide to produce the compound (V) of the present invention (Rc = OR ² ,
(Where Z = N).

[0018]

[Chemical 6]

(4) Scheme 4 uses (IV) as the first step.
Is oxidized to a compound (VI), and as a second step, (VI) is reacted with a metal alkoxide, an amine or a metal mercaptide to give a corresponding compound (V) of the present invention (Rc = OR ² ,
Z = N), (X) (Rc = N (R ³ ) R ⁴ , Z =
N)) or (IV ′) (Rc = SR ² , Z = N).

[0020]

[Chemical 7]

(5) Scheme 5 is the first step (VII)
To react with amidine derivative to give compound (VIII)
As a step, (VIII) is reacted with a chlorinating agent to give a chlorinated body (IX), and as a third step, (IX) is reacted with a metal mercaptide, a metal alkoxide or an amine to give a corresponding compound (IV) (Rc = SR) of the present invention. ¹ , when Z = N), (V) (when Rc = OR ² , Z = N) or (X) (when Rc = N (R ³ ) R ⁴ , Z = N) Represent

[0022]

[Chemical 8]

(6) The scheme 6 is the reaction of the 5-acylpyrimidine derivative (III) with the acyl derivative in the presence of a base, and subsequently with ammonium acetate to react the compound of the present invention (XI) (Rc = SR ¹ , Z = CH).

[0024]

[Chemical 9]

(7) The scheme 7 is the reaction of (XI) with alkoxide to give the compound (XII) (Rc = OR ² , Z of the present invention.
In the case of = CH).

[0026]

[Chemical 10]

(8) The scheme 8 is (XI) as the first step.
Is oxidized to a compound (XIII), and the second step (XII
I) is reacted with a metal alkoxide, an amine or a metal mercaptide to give the corresponding compound (XII) of the present invention (Rc = O
R ² and Z = CH), (XIV) (Rc = N (R ³ ) R
⁴ , when Z = CH) or (XI ') (Rc = SR ² , Z
In the case of = CH).

The synthetic examples of the compound of the present invention and the intermediate will be specifically described below as Examples, but the present invention is not limited thereto.

[0029]

【Example】

Example 1 3-Methoxymethylene-1,1,1-trifluoro-
Synthesis of 2,4-pentanedione

[0030]

[Chemical 11]

500 g of 60 g of trifluoroacetylacetone, 42 g of methyl orthoformate and 91 g of acetic anhydride were used.
It was placed in an eggplant flask having a capacity of ml. The eggplant flask was equipped with a Gene Stark apparatus, and refluxed for about 2 hours while distilling off methyl acetate. After completion of the reaction, the mixture was cooled to room temperature and distilled under reduced pressure to obtain 33.7 g of the desired product as a pale red liquid. Boiling point 90-115 [deg.] C./4 mmHg.

¹ H-NMR δ (ppm) [solve
nt]; 2.30, 2.40 (each s, both peaks combined 3H, COC H ₃ ), 4.11, 4.15 (each s,
Both peaks combined 3H, OC H ₃ ), 7.66, 7.8
4 (each s, 1H for both peaks combined, C = C H O) [C
DCl _3] Example 2 3-ethoxymethylene-1,1,1-trifluoro -
Synthesis of 2,4-pentanedione

[0033]

[Chemical 12]

100 g of trifluoroacetylacetone,
Ethyl orthoformate 134.5 g and acetic anhydride 185.
6 g was put in a 500 ml eggplant flask and refluxed for 2 hours.
Subsequently, ethanol and ethyl acetate were distilled off under reflux with a Gene Stark apparatus attached. The reaction solution was distilled under reduced pressure to obtain 78.5 g of the desired product as a liquid. Boiling point 82-8
3 ° C / 0.2 mmHg.

¹ H-NMR δ (ppm) [solve
nt]; 1.45 (t, J = 7Hz , 3H, CH 2 C H
_3), 2.31,2.42 (each s, both peaks combined _{3H, COC H 3), 4.36} (q, J = 7Hz, 2
H, C H ₂ CH ₃ ), 7.70, 7.95 (each s, both peaks combined 1 H, C = C H O) [CDCl ₃ ] [Example 3] 5-acetyl-4-trifluoromethyl Pyrimidine synthesis

[0036]

[Chemical 13]

1.3 g of sodium metal was added to 100 ml of dehydrated ethanol to prepare sodium methoxide, and then 5.58 g of formamidine acetate which had been sufficiently dried.
Was added and stirred for 5 minutes. Furthermore, 3-methoxymethylene-
1,1,1-trifluoro-2,4-pentanedione 1
0 g was diluted with 50 ml of dehydrated ethanol and added dropwise. After refluxing for 2.5 hours, ethanol was distilled off under reduced pressure, saturated saline was added, and the mixture was extracted with ether. After distilling off the solvent, the residue was subjected to column chromatography (developing solvent: CHCl ₃ ).
The product was purified by the method described above to obtain 5.4 g of the desired product as an oil.

¹ H-NMR δ (ppm) [solve
nt]; 2.68 (s, 3H, COC H 3), 9.07
(S, 1H), 9.48 ( s, 1H) [CDCl _3] Example 4 5- [2,2-bis (methylthio) vinyl carbonyl]
Synthesis of 4-trifluoromethylpyrimidine

[0039]

[Chemical 14]

10.2 g of 5-acetyl-4-trifluoromethylpyrimidine and 4.9 g of carbon disulfide were dissolved in 80 ml of dimethylformamide and cooled to 0 ° C. with ice water. To this mixed solution, 4.3 g of 60% sodium hydride was gradually added, and the mixture was stirred at room temperature for 1 hour. Then methyl iodide 1
8.3 g was added dropwise and stirring was continued for another 2 hours. The reaction solution was poured into 200 ml of ice water and extracted with ethyl acetate,
It was dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting residue was subjected to column chromatography (developing solvent: CHC
Purification by l _3), to give the desired product 3.45g as a solid.
Melting point 121-122 [deg.] C.

¹ H-NMR δ (ppm) [solve
nt]; 2.49 (s, 3H, SC H 3), 2.57
_{(S, 3H, SC H 3} ), 6.27 (s, 1H, COC
H C), 8.93 (s, 1H), 9.31 (s, 1H)
[CDCl _3] Example 5 Synthesis of 5 [2- (4-fluorophenyl) -6-methylthio-4-pyrimidyl] -4-trifluoromethyl pyrimidine.

[0042]

[Chemical 15]

5- [2,2-bis (methylthio) vinylcarbonyl] -4-trifluoromethylpyrimidine 0.
45 g and 4-fluorophenylamidine hydrochloride 0.3 g
Was dissolved in t-butanol, and 0.2 g of potassium t-butoxide was added. After refluxing for 3 hours, the solvent was evaporated, water was added, and the mixture was extracted with ethyl acetate. After drying over anhydrous sodium sulfate, the solvent was distilled off to obtain a crude product. This was isolated and purified by thin layer chromatography (developing solvent: CHCl ₃ ) to obtain 0.23 g of the desired product as crystals. Melting point 112-
113 ° C.

¹ H-NMR δ (ppm) [solve
nt]; 2.70 (s, 3H, SC H 3), 6.90~
7.30 (m, 3H), 8.30 to 8.65 (m, 2
H), 9.01 (s, 1H), 9.38 (s, 1H)
[CDCl ₃ ] [Example 6] Synthesis of 5-acetyl-4-trifluoromethylpyrimidine

[0045]

[Chemical 16]

4.8 g of sodium metal was added to 150 ml of dry ethanol under ice cooling to prepare sodium ethoxide, and formamidine acetate salt 2 which had been completely dried was added.
0.8 g was added. Further, 40 g of 1,1,1-trifluoro-3-ethoxymethylene-2,4-pentanedione was diluted with 50 ml of dry ethanol at −10 ° C. and slowly added dropwise. After heating under reflux for 2 hours and cooling with ice, the solid was filtered off and the solvent was distilled off under reduced pressure. The residue was distilled under reduced pressure to obtain the desired product 28.
5 g were obtained as a liquid. Boiling point 65-66 ° C / 3.5mm
Hg. Example 7 Synthesis of 1-chloro-1,1-difluoro-3-ethoxymethylene-2,4-pentanedione

[0047]

[Chemical 17]

1-chloro-1,1-difluoro-1,3
-Pentanedione 50 g, orthoformic acid ethyl ester 6
A mixed solution of 0 g and acetic anhydride 82 g was refluxed for 2 hours. Furthermore, the Gene Stark device is attached, and further 4
While heating under reflux for about 100 ml during this period was distilled off. After cooling, it was distilled under reduced pressure to obtain 32.2 g of the desired product as a pale red liquid. Boiling point 95-118 [deg.] C./1.6 mmHg.

[0049]¹1 H-NMR δ (ppm) [solve
nt]; 1.41, 1.45 (each t,J= 8Hz, both
3H, CH including peaks₂CH ₃), 2.28, 2.
41 (each s, both peaks combined 3H, COCH ₃),
4.32, 4.36 (q,J= 8 Hz, both peaks combined
2H, CH ₂CH ₃), 7.74, 7.84 (each
S, 1H for both peaks, C = CHO) [CDCl
₃Example 8 5-Acetyl-4-chlorodifluoromethylpyrimidine
Synthesis of

[0050]

[Chemical 18]

0.9 g of metallic sodium was added to 50 ml of dry ethanol under ice cooling to prepare sodium ethoxide, and then 8.4 g of formamidine acetate completely dried by a vacuum pump was added. Further under ice cooling, 1-chloro-
1,1-difluoro-3-ethoxymethylene-2,4-
8 g of pentanedione was diluted with 20 ml of dry ethanol and then added dropwise. After heating under reflux for 1.5 hours, the mixture was allowed to cool, water was added, and the mixture was extracted with ether. After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, distillation under reduced pressure was performed, and then 2.5 g of the target product was obtained as a liquid by column chromatography (developing solvent: CHCl ₃ ). Boiling point 65-70 ° C / 1.3
mmHg, n _D ^20.7 1.4787 ¹ H-NMR δ (ppm) [solvent];
65 (t, J = 1Hz, 3H, COC H 3), 8.90
(S, 1H), 9.42 ( s, 1H) [CDCl _3] Example 9 5- [2,2-bis (methylthio) vinyl carbonyl]
Synthesis of 4-chlorodifluoromethylpyrimidine

[0052]

[Chemical 19]

7.3 g of 5-acetyl-4-chlorodifluoromethylpyrimidine and 3.23 g of carbon disulfide were dissolved in 80 ml of dry dimethylformamide, and 1.78 g of sodium hydride was slowly added under ice cooling and the mixture was stirred for 1 hour. . After adding 50 ml of dry dimethylformamide, 12.06 g of methyl iodide was slowly added dropwise, and after stirring overnight, 300 ml of ice water was added and the mixture was extracted with ethyl acetate.
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure. Column chromatography from crude (developing solvent: CHCl
_{According to 3} ), 1.08 g of the desired product was obtained as a solid. Melting point 1
36-140 ° C. Example 10 Synthesis of 5- [6-methylsulfonyl-2- (4-trifluoromethylphenyl) -4-pyrimidyl] -4-trifluoromethylpyrimidine

[0054]

[Chemical 20]

5- [6-methylthio-2- (4-trifluoromethylphenyl) -in 100 ml of chloroform
4-pyrimidyl] -4-trifluoromethylpyrimidine 1.2 g and metachloroperbenzoic acid 1.7 g were added,
The mixture was stirred at room temperature for 30 minutes. The mixture was washed twice with 100 ml of saturated aqueous sodium hydrogen carbonate solution, then twice with water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The remaining solid was recrystallized from isopropyl alcohol to give the desired product 1.1.
g was obtained as crystals. Melting point 156-157 [deg.] C. [Example 11] Synthesis of 5- [6-ethoxy 2- (4-trifluoromethylphenyl) -4-pyrimidyl] -4-trifluoromethylpyrimidine

[0056]

[Chemical 21]

To 50 ml of dry ethanol, 0.1 g of metallic sodium and 0.4 g of 5- [6-methylthio-2- (4-trifluoromethylphenyl) -4-pyrimidyl] -4-trifluoromethylpyrimidine were added, and the mixture was added for 3 hours. Heated to reflux. After cooling, 10 ml of water was added, the solvent was distilled off under reduced pressure, and the residue was extracted twice with 30 ml of chloroform.
The extraction solution was washed twice with water, dried over anhydrous sodium sulfate,
The solvent was distilled off under reduced pressure. The remaining solid was purified by preparative thin layer chromatography (developing solvent: CHCl ₃ ) to obtain 0.3 g of the desired product as a solid. Melting point 101-103 ° C

Example 12 Synthesis of 5- [6-methylamino-2- (4-trifluoromethylphenyl) -4-pyrimidyl] -4-trifluoromethylpyrimidine

[0059]

[Chemical formula 22]

0.4 g of 5- [6-methylsulfonyl-2- (4-trifluoromethylphenyl) -4-pyrimidyl] -4-trifluoromethylpyrimidine and 50 m of a 50% methylamine aqueous solution in 50 ml of chloroform.
1 was added, and the mixture was stirred at room temperature for 1 hour. The mixture was washed twice with water, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. The remaining solid was purified by preparative thin layer chromatography (developing solvent: CHCl ₃ ) to obtain 0.3 g of the desired product as a solid. Melting point 112-114 ° C

Example 13 4-Chlorodifluoromethyl-5- [6-methylthio-2
Synthesis of-(4-trifluoromethylphenyl) -4-pyrimidyl] pyrimidine

[0062]

[Chemical formula 23]

0.45 g of 5- [2,2-bis (methylthio) vinylcarbonyl] -4-chlorodifluoromethylpyrimidine and 0.37 g of 4-trifluoromethylbenzamidine hydrochloride were dissolved in 10 ml of t-butanol to prepare potassium t. -0.28 g of butoxide was added and heating under reflux was continued for 8 hours. After the solvent was distilled off under reduced pressure, water was added and the mixture was extracted with ethyl acetate and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the crude product was isolated by preparative thin layer chromatography (developing solvent: CHCl ₃ ) to obtain 0.2 g of the desired product as a solid. Melting point 81-84 [deg.] C.

Example 14 Synthesis of 5- [6-methylthio-2- (4-trifluoromethylphenyl) -4-pyrimidyl] -4-trifluoromethylpyrimidine

[0065]

[Chemical formula 24]

2.8 g of 4-trifluoromethylbenzamidine hydrochloride and potassium t in 70 ml of t-butanol.
-Butoxide 1.6 g was added and stirred at room temperature for 15 minutes.
Thereafter, 3 g of 5- [2,2-bis (methylthio) vinylcarbonyl] -4-trifluoromethylpyrimidine was added, and the mixture was heated under reflux for 3 hours. After distilling off the solvent under reduced pressure,
It was extracted with ethyl acetate, washed twice with water, and dried over anhydrous sodium sulfate. After the solvent was distilled off under reduced pressure, the residue was purified by column chromatography (developing solvent: CHCl ₃ ),
2.5 g of the target product was obtained as a solid. Melting point 93-94 [deg.] C.

Structural formulas and physical properties of the compounds of the present invention synthesized according to the above Examples are shown in Tables 1 and 2 including the above Examples. The structures and physical properties of the intermediates are shown in Tables 3-1 and 3-2. [Table 1]

[0068]

[Chemical 25]

[0069]

[Table 1] ─────────────────────────────────── Compound Ra Rb Rc Z No. ─────────────────────────────────── 1 CF ₃ 4-CF ₃ -phenyl SCH ₃ N 2 CF ₃ 4-CF ₃ -phenyl OCH ₂ CH ₂ CH ₃ N 3 CF ₃ 4-F-phenyl SCH ₃ N 4 CH ₃ 4-F-phenyl SCH ₃ N 5 CF ₃ 4-CF ₃ -phenyl N (CH ₃ ) ₂ N 6 CF ₃ 4-CF ₃ -phenyl NHC ₂ H ₅ N 7 CF ₃ 4-CF ₃ -phenyl NHCH ₃ N 8 CF ₃ 4-CF ₃ -phenyl OC ₂ H ₅ N 9 CF ₂ Cl 4-CF _3- phenyl SCH ₃ N 10 CF ₃ 4-CF ₃ -phenyl OCH ₃ N 11 CF ₃ 4-F-phenyl N (CH ₃ ) ₂ N 12 CF ₃ 4-F-phenyl NHCH ₃ N 13 CF ₃ 4-F-phenyl NHC ₂ H ₅ N 14 CF ₃ 4-F-phenyl OCH ₃ N 15 CF ₃ 4-F-phenyl OC ₂ H ₅ N 16 CF ₃ 3,4-F ₂ -phenyl N (CH ₃ ) ₂ N 17 CF ₃ 3, _{4 -F 2 -phenyl NHCH 3 N 18} CF 3 3,4 -F 2 -phenyl SCH 3 N 19 CF 3 4-Bu t -phenyl SCH 3 N 20 CF 3 4-Br-phenyl SCH 3 N ──── ───────────────────────────────

[0070]

[Table 2] [Table 2] ─────────────────────────────────── Compound ¹ H-NMR δ (Ppm) No. [Solvent] Physical property ─────────────────────────────────── 1 2.74 (s, 3H, SC H ₃ ), 7.22 (s, 1H), 7.66 (d, J = 8 Hz, 2H, benzene ring), 8.53 (d, J = 8 Hz, 2H, benzene ring), 9.02 ( s, 1H), 9.39 (s, 1H) [CDCl ₃ ] melting point 94-96 ° C ───────────────────────────── ─────── 2 1.10 (t, J = 8 Hz, 3 H), 1.75 to 2.15 (m, 2 H), 4.55 (t, J = 6 Hz, 2 H), 6.85 (S, 1H), 7.70 (d, J = 8 Hz, 2H, benzene ring), 8.55 (d, J = 8 Hz, 2H, benzene ring), 9.40 (s, 1H) [CDCl ₃ ] Melting point 119-12 ℃ ─────────────────────────────────── 3 2.70 (s, 3H , SC H 3), 6.90~7.30 (m, 3H), 8.30~8.65 (m, 2H), 9.01 (s, 1H), 9.38 (s, 1H) [CDCl _3] mp 112- 113 ℃ ───────────────────────────────────

[0071]

[Table 3] [Continued Table 2] ─────────────────────────────────── Compound ¹ H-NMR δ (ppm) No. [Solvent] Physical property ─────────────────────────────────── 4 2.70 (s, 6H) , 6.90 to 7.35 (m, 3H), 8.25 to 8.65 (m, 2H), 8.72 (s, 1H), 9.08 (s, 1H) [CDCl ₃ ] melting point 163. -168 ° C ─────────────────────────────────── 5 3.22 (s, 6H, N (C _{H 3) 2), 6.51 (} s, 1H), 7.66 (d, J = 8Hz, 2H, benzene ring), 8.55 (d, J = 8Hz, 2H, benzene ring), 9.09 (S, 1H), 9.38 (s, 1H) [CDCl ₃ ] melting point 134-135 ° C ──────────────────────────── ──────── 6 1.31 (t, J = _{Hz, 3H, NHCH 2 C H} 3), 3.55 (m, 2H, NHC H 2 CH 3), 5.63 (br s, 1H, N H C 2 H 5), 6.43 (s, 1H ), 7.67 (d, J = 8Hz, 2H, benzene ring), 8.53 (d, J = 8Hz, 2H, benzene ring), 9.08 (s, 1H), 9.37 (s, 1H) ) [CDCl ₃ ] melting point 75-76 ° C ────────────────────────────────────

[0072]

[Table 4] [Continued Table 2] ─────────────────────────────────── Compound ¹ H-NMR δ (ppm) No. [Solvent] Physical property ─────────────────────────────────── 7 3.07 (d, J = _{6Hz, 3H, NHC H 3)} , 4.53 (br s, 1H), 6.43 (s, 1H), 7.66 (d, J = 8Hz, 2H, benzene ring), 8.52 (d, J = 8 Hz, 2H, benzene ring), 9.11 (s, 1H), 9.42 (s, 1H) [CDCl ₃ ] melting point 112-114 ° C ─────────────── ───────────────────── 8 1.51 (t, J = 7Hz, 3H, OCH 2 C H 3), 4.65 (q, J = 7Hz , 2H, OC H ₂ CH ₃ ), 6.84 (s, 1H), 7.19 (d, J = 9 Hz, 2H, benzene ring), 8.58 (d, J = 9 Hz, 2H, benzene ring) , 9 08 (s, 1H), 9.41 (s, 1H) [CDCl _3] melting point 101-103 ℃ ────────────────────────── ────────── 9 2.76 (s, 3H, SC H 3), 7.29 (s, 1H), 7.70 (d, J = 8Hz, 2H, benzene ring), 8 80 (d, J = 8 Hz, 2H, benzene ring), 8.90 (s, 1H), 9.40 (s, 1H) [CDCl ₃ ] melting point 81-84 ° C ─────────── ────────────────────────────

[0073]

[Table 5] [Continued Table 2] ─────────────────────────────────── Compound ¹ H-NMR δ (ppm) No. [Solvent] Physical property ─────────────────────────────────── 10 4.20 (s, 3H, OC H ₃ ), 6.91 (s, 1H), 7.74 (d, J = 8 Hz, 2H, benzene ring), 8.63 (d, J = 8 Hz, 2H, benzene ring), 9.13 ( s, 1H), 9.48 (s, 1H) [CDCl ₃ ] Melting point Viscous oil ───────────────────────────── ────── 11 3.19 (s, 6H, N (C H ₃ ) ₂ ), 6.42 (s, 1H), 7.03 (dd, J = 9 Hz, 2H, benzene ring), 8 .38 (dd, J = 9 Hz, 6 Hz, 2H, benzene ring), 9.02 (s, 1H), 9.32 (s, 1H) [CDCl ₃ ] melting point 163-165 ° C. ───────── ──── ───────────────────────── 12 3.08 (d, J = 5 Hz, 3H, NHC H ₃ ), 5.23 (br s, 1H, NH CH ₃ ), 6.36 (s, 1H), 7.22 (dd, J = 9Hz, 2H, benzene ring), 8.40 (dd, J = 9Hz, 6Hz, 2H, benzene ring) , 9.06 (s, 1H), 9.36 (s, 1H) [CDCl ₃ ] melting point 188-190 ° C ──────────────────────── ─────────────

[0074]

[Table 6] [Continued Table 2] ─────────────────────────────────── Compound ¹ H-NMR δ (ppm) No. [Solvent] Physical property ─────────────────────────────────── 13 1.32 (t, J = _{7Hz, 3H, NHCH 2 C H} 3), 3.48 (m, 2H, NHC H 2 CH 3), 5.23 (br s, 1H, N H CH 2 CH 3), 6.32 (s, 1H ) 7.14 (dd, J = 9 Hz, 2H, benzene ring), 8.34 (dd, J = 9 Hz, 6 Hz, 2H, benzene ring), 9.03 (s, 1H), 9.33 (s, 1H) [CDCl ₃ ] melting point 141-143 ° C. ───────────────────────────────────── 14 4. 14 (s, 3H, OC H 3), 6.76 (s, 1H), 7.10 (dd, J = 9Hz, 2H, benzene ring), 8.45 (dd, J = 9Hz, 6Hz 2H, benzene ring), 9.03 ( s, 1H), 9.39 (s, 1H) [CDCl _3] mp 97- 98 ° C. ────────────────── ──────────────────

[0075]

[Table 7] [Continued Table 2] ─────────────────────────────────── Compound ¹ H-NMR δ (ppm) No. [Solvent] Physical property ─────────────────────────────────── 15 1.49 (t, J = _{7Hz, 3H, OCH 2 C H} 3), 4.64 (q, J = 7Hz, 2H, OC H 2 CH 3), 6.75 (s, 1H), 7.10 (dd, J = 9Hz, 2H , Benzene ring), 8.44 (dd, J = 9 Hz, 6 Hz, 2H, benzene ring), 9.04 (s, 1H), 9.40 (s, 1H) [CDCl ₃ ] melting point 95-97 ° C. ─────────────────────────────────── 16 3.22 (s, 6H, N (C H 3) ₂ ), 6.46 (s, 1H), 7.20 (m, 1H, benzene ring), 8.15 (m, 2H, benzene ring), 9.04 (s, 1H), 9.36 (s , 1H) [CDC l ₃ ] melting point 153-154 ° C. ───────────────────────────────────── 17 3.04 (d , J = 5 Hz, 3H, NHC H ₃ ), 5.50 (br s, 1H, NH CH ₃ ), 6.51 (s, 1H), 7.20 (m, 1H, benzene ring), 8. 21 (m, 2H, benzene ring), 9.05 (s, 1H), 9.35 (s, 1H) [CDCl ₃ + DMSO-d ₆ ] melting point 175-176 ° C ──────────── ──────────────────────────

[0076]

[Table 8] [Continued Table 2] ─────────────────────────────────── Compound ¹ H-NMR δ (ppm) No. [Solvent] Physical property ─────────────────────────────────── 18 2.72 (s, 3H, SC H ₃ ), 7.22 (s, 1H), 7.26 (m, 1H, benzene ring), 8.25 (m, 2H, benzene ring), 9.03 (s, 1H), 9.40. (S, 1H) [CDCl ₃ ] melting point 129-131 ° C ───────────────────────────────────── 19 1.35 (s, 9H, C (C H 3) 3), 2.71 (s, 3H, SC H 3), 7.14 (s, 1H), 7.44 (d, J = 8Hz, 2H, benzene ring), 8.38 (d, J = 8Hz, 2H, benzene ring), 9.03 (s, 1H), 9.37 (s, 1H) [CDCl ₃ ] melting point viscous oil ─── ───────── ─────────────────────── 20 2.73 (s, 3H, SC H 3), 2.74 (s, 1H), 7.09 ( d, J = 9 Hz, 2H, benzene ring), 8.36 (d, J = 9 Hz, 2H, benzene ring), 9.07 (s, 1H), 9.43 (s, 1H) [CDCl ₃ ] melting point 131-133 ℃ ────────────────────────────────────

[Table 3-1]

[0078]

[Chemical formula 26]

[0079]

[Table 9] ─────────────────────────────────── Compound Ra ¹ H-NMR δ (ppm) No ． [Solvent] Physical property ─────────────────────────────────── 101 CH ₃ 2.50 (s, 3H), 2.54 (s, 3H ), 2.64 (s, 3H), 6.28 (s, 1H, COC H C), 8.78 (s, 1H), 9.00 (s, 1H ) [CDCl ₃ ] melting point 126-128 ° C. ─────────────────────────────────── 102 CF ₃ 2. 49 (s, 3H, SC H 3), 2.57 (s, 3H, SC H 3), 6.27 (s, 1H, COC H C), 8.93 (s, 1H), 9.31 ( s, 1H) [CDCl ₃ ] melting point 121-122 ° C ─────────────────────────────────── 103 CF ₂ Cl 2.49 (s, 3H, _{C H 3), 2.52 (s} , 3H, SC H 3), 6.18 (s, 1H, COC H C), 8.88 (s, 1H), 9.30 (s, 1H) [CDCl ₃ ] Melting point 136-140 ° C ─────────────────────────────────────

[Table 3-2]

[0081]

[Chemical 27]

[0082]

[Table 10] ─────────────────────────────────── Compound Ra, Rb, Z No. ¹ H-NMR δ (ppm) [Solvent] Physical properties ──────────────────────────────────── 201 _{CF 3, 4-CF 3 -phenyl} , N 3.40 (s, 3H, SO 2 C H 3), 7.74 (d, J = 8Hz, 2H, benzene ring), 8.10 (s, 1H) , 8.61 (d, J = 8 Hz, 2H, benzene ring), 9.13 (s, 1H), 9.52 (s, 1H) [CDCl ₃ ] melting point 156-157 ° C. ───────── _{──────────────────────────── 202 CF 3, 4-F} -phenyl, N 3.51 (s, 3H, SO 2 C H ₃ ), 7.30 (dd, J = 9 Hz, 2H, benzene ring), 8.33 (s, 1H), 8.52 (dd, J = 9 Hz, 6 Hz, 2H, benzene ring) ), 9.39 (s, 1H), 9.52 (s, 1H) [CDCl ₃ + DMSO-d ₆ ] Melting point 169-170 ° C ─────────────────── ───────────────── The compounds of the present invention synthesized according to the above schemes or examples are shown in Table 4 including the compounds synthesized in the above examples. The invention is not limited to these.

[Table 4]

[0084]

[Chemical 28]

[0085]

[Chemical 29]

[0086]

[Chemical 30]

[0087]

[Chemical 31]

[0088]

[Chemical 32]

[0089]

[Chemical 33]

[0090]

[Table 11] ────────────────────────────── Rb Rc ─────────────── ──────────────── phenyl SCH ₃ 4-F-phenyl SCH ₃ 4-Cl-phenyl SCH ₃ 4-Br-phenyl SCH ₃ 4-I-phenyl SCH ₃ 4-CF ₃ -phenyl SCH ₃ 3-F-phenyl SCH ₃ 3-Cl-phenyl SCH ₃ 3-Br-phenyl SCH ₃ 3-I-phenyl SCH ₃ 3-CF ₃ -phenyl SCH ₃ 2-F-phenyl SCH ₃ 2- Cl-phenyl SCH ₃ 2-Br-phenyl SCH ₃ 2-I-phenyl SCH ₃ 2-CF ₃ -phenyl SCH ₃ 2-CH ₃ -phenyl SCH ₃ 3-CH ₃ -phe nyl SCH ₃ 4-CH ₃ -phenyl SCH ₃ 4-OCF ₃ -phenyl SCH ₃ 4-OCF ₂ H-phenyl SCH ₃ 4-F-phenyl OCH ₃ 4-Cl-phenyl OCH ₃ ───────── ──────────────────────

[0091]

[Table 12] [Continued Table 4] ────────────────────────────── Rb Rc ───────── ────────────────────── 4-Br-phenyl OCH ₃ 4-CF ₃ -phenyl OCH ₃ 4-OCF ₃ -phenyl OCH ₃ 2-pyridyl SCH _{3 3-pyridyl SCH 3 4-pyridyl} SCH 3 2-thienyl SCH 3 3-thienyl SCH 3 benzyl SCH 3 5-CF 3 -2-pyridyl SCH 3 5-Cl-2-pyridyl SCH 3 6-CF 3 -3-pyridyl _{SCH 3 6-Cl-3-} pyridyl SCH 3 4-pyridyl OCH 3 5-Cl-2-pyridyl OCH 3 5-CF 3 -2-pyridyl OCH 3 4-C _{F 3 -phenyl SC 2 H 5 4} -Cl-phenyl SC 2 H 5 4-F-phenyl SC 2 H 5 4-Br-phenyl SC 2 H 5 4-OCF 3 -phenyl SC 2 H 5 4-CF 3 - phenyl OC ₂ H ₅ ───────────────────────────────

[0092]

[Table 13] [Continued Table 4] ────────────────────────────── Rb Rc ───────── ────────────────────── 4-Cl-phenyl OC ₂ H ₅ 4-F-phenyl OC ₂ H ₅ 4-Br-phenyl OC ₂ H ₅ 4 _{-OCF 3 -phenyl OC 2 H 5 4} -Cl-phenyl SCH (CH 3) 2 4-CF 3 -phenyl SCH (CH 3) 2 4-F-phenyl SCH (CH 3) 2 4-Cl-phenyl OCH ( CH ₃ ) ₂ 4-CF ₃ -phenyl OCH (CH ₃ ) ₂ 4-F-phenyl OCH (CH ₃ ) ₂ 2-F-4-CF ₃ -phenyl SCH ₃ 3-F-4-CF ₃ -phenyl SCH ₃ 3,4-di-F-phenyl SCH ₃ 2,4-di- _{F-phenyl SCH 3 3,4-di} -Cl-phenyl SCH 3 2,4-di-Cl-phenyl SCH 3 2-F-4-Cl-phenyl SCH 3 4-Cl-phenyl OC (CH 3) 3 4 _{-F-phenyl OC (CH 3)} 3 4-CF 3 -phenyl OC (CH 3) 3 4-Cl-phenyl N (CH 3) 2 4-F-phenyl N (CH 3) 2 ────── ────────────────────────

[0093]

[Table 14] [Continued Table 4] ──────────────────────────────── Rb Rc ─────── ────────────────────────── 4-CF ₃ -phenyl N (CH ₃ ) ₂ 4-Br-phenyl N (CH ₃ ) ₂ 4 _{-Cl-phenyl NHCH 3 4-F} -phenyl NHCH 3 4-CF 3 -phenyl NHCH 3 4-Br-phenyl NHCH 3 4-F-phenyl NHC 2 H 5 4-Cl-phenyl NHC 2 H 5 4-Br- _{phenyl NHC 2 H 5 4-CF} 3 -phenyl NHC 2 H 5 4-F-phenyl NCH (CH 3) 2 4-Cl-phenyl NCH (CH 3) 2 4-Br-phenyl NCH (CH 3) 2 4- CF ₃ -phenyl NCH (CH ₃ ) ₂ 4-F-phenyl NHCH ₂ CH ₂ CH ₃ 4-Cl-phenyl NHCH ₂ CH ₂ CH ₃ 4-Br-phenyl NHCH ₂ CH ₂ CH ₃ 4-CF ₃ -phenyl NHCH ₂ CH ₂ CH ₃ 4-F _{-phenyl NHC (CH 3) 3 4} -Cl-phenyl NHC (CH 3) 3 4-Br-phenyl NHC (CH 3) 3 4-CF 3 -phenyl NHC (CH 3) 3 ──────── ────────────────────────

[0094]

[Table 15] [Continued Table 4] ────────────────────────────────── Rb Rc ──── ────────────────────────────── 4-F-phenyl NHCH ₂ CH = CH ₂ 4-Cl-phenyl NHCH ₂ CH = CH ₂ 4-Br-phenyl NHCH ₂ CH = CH ₂ 4-CF ₃ -phenyl NHCH ₂ CH = CH ₂ 4-F-phenyl NHCH ₂ C≡CH 4-Cl-phenyl NHCH ₂ C≡CH 4-Br-phenyl _{NHCH 2 C≡CH 4-CF 3 -phenyl} NHCH 2 C≡CH 4-F-phenyl N (C 2 H 5) 2 4-Cl-phenyl N (C 2 H 5) 2 4-Br-phenyl N (C ₂ H ₅ ) ₂ 4-CF ₃ -phenyl N (C ₂ H ₅ ) ₂ 4-F-phenyl NH ₂ 4-Cl-phenyl NH ₂ 4-Br-phenyl NH ₂ 4-CF ₃ -phenyl NH ₂ 4-F-phenyl N (CH (CH ₃ ) ₂ ) ₂ 4-Cl- phenyl N (CH (CH ₃ ) ₂ ) ₂ 4-Br-phenyl N (CH (CH ₃ ) ₂ ) ₂ 4-CF ₃ -phenyl N (CH (CH ₃ ) ₂ ) ₂ 4-F-phenyl N (CH ₂ CH ₂ CH ₃ ) ₂ 4-Cl-phenyl N (CH ₂ CH ₂ CH ₃ ) ₂ ───────────────────────────── ──────

[0095]

[Table 16] [Continued Table 4] ────────────────────────────────── Rb Rc ──── ────────────────────────────── 4-Br-phenyl N (CH ₂ CH ₂ CH ₃ ) ₂ 4-CF ₃ − phenyl N (CH ₂ CH ₂ CH ₃ ) ₂ 4-F-phenyl N (CH ₂ CH = CH ₂ ) ₂ 4-Cl-phenyl N (CH ₂ CH = CH ₂ ) ₂ 4-Br-phenyl N (CH _2). CH = CH ₂ ) ₂ 4-CF ₃ -phenyl N (CH ₂ CH = CH ₂ ) ₂ 4-F-phenyl N (CH ₂ C≡CH) ₂ 4-Cl-phenyl N (CH ₂ C≡CH) ₂ 4-Br-phenyl N (CH 2 C≡CH) 2 4-CF 3 -phenyl N (CH 2 C≡CH) 2 4-F-phenyl _{1 4-Cl-phenyl Q 1} 4-Br-phenyl Q 1 4-CF 3 -phenyl Q 1 4-F-phenyl Q 2 4-Cl-phenyl Q 2 4-Br-phenyl Q 2 4-CF 3 -phenyl Q ₂ 4-F-phenyl Q ₃ 4-Cl-phenyl Q ₃ 4-Br-phenyl Q ₃ 4-CF ₃ -phenyl Q ₃ ──────────────────── ───────────────

[0096]

[Table 17] [Continued Table 4] ────────────────────────────── Rb Rc ───────── ────────────────────── 4-F-phenyl Q ₄ 4-Cl-phenyl Q ₄ 4-Br-phenyl Q ₄ 4-CF ₃ -phenyl Q _{4 3,4-di-F-phenyl} OCH 3 3,4-di-F-phenyl OC 2 H 5 3,4-di-F-phenyl N (CH 3) 2 3,4-di-F-phenyl NHCH ₃ 3,4-di-F-phenyl NHC ₂ H ₅ ───────────────────────────────

However, Q ₁ , Q ₂ , Q ₃ and Q _{4 in} Table ₄ represent the following.

[0098]

[Chemical 34]

In applying the compound of the present invention as a herbicide, generally, a suitable carrier, for example, a solid carrier such as clay, talc, bentonite, diatomaceous earth, white carbon or the like, water, alcohols (isopropanol, butanol, benzyl alcohol, fluroalcohol), Furyl alcohol etc.), aromatic hydrocarbons (toluene, xylene etc.), ethers (anisole etc.), ketones (cyclohexanone, isophorone etc.), esters (butyl acetate etc.), acid amides (N-methylpyrrolidone etc.) ) Or halogenated hydrocarbons (chlorobenzene etc.) and other liquid carriers can be mixed and applied, and if desired, surfactants, emulsifiers, dispersants, penetrants, spreading agents, thickeners, antifreeze. Agents, anti-caking agents, stabilizers, etc., liquids, emulsions, wettable powders,
It can be put into practical use in any dosage form such as a dry flowable agent, a flowable agent, a powder agent, and a granule agent.

If desired, the compound of the present invention may be mixed with other herbicides, various insecticides, fungicides, plant growth regulators, synergists and the like at the time of formulation or spraying. In particular,
By applying it in combination with other herbicides, it is expected that the cost will be reduced by reducing the amount of the applied drug, the herbicidal spectrum will be expanded by the synergistic action of the mixed agents, and a higher herbicidal effect will be expected. At this time, it is possible to combine a plurality of known herbicides at the same time. Examples of the type of herbicide used in combination with the compound of the present invention include, for example, Farm Chemicals Handbook (F
arm Chemicals Handbook) 1991 version.

The application dose of the compound of the present invention varies depending on the application scene, application time, application method, cultivated crop, etc., but generally 0.0001 to 10 per hectare (ha) as an active ingredient amount.
About kg, preferably about 0.001 to 5 kg is suitable. Next, specific examples of formulation of the preparation when the compound of the present invention is used are shown. However, the compounding examples of the present invention are not limited to these. In the following formulation examples, "part" means part by weight.

[Wettable powder] Compound of the present invention ─────── 5-80 parts Solid carrier ──────── 10-85 parts Surfactant ─────── 1-10 parts Others ─────── 1-5 parts Other examples include anti-caking agents.

[Emulsion] Compound of the present invention ─────── 1-30 parts Liquid carrier ─────── 30-95 parts Surfactant ─────── 5-15 parts

[Flowable agent] Compound of the present invention ─────── 5 to 70 parts Liquid carrier ─────── 15 to 65 parts Surfactant ─────── 5 to 12 parts Others ─ ────── 5-30 parts Others include, for example, antifreezing agents, thickeners and the like.

[Granular wettable powder (dry flowable agent)] Compound of the present invention ─────── 20 to 90 parts Solid carrier ─────── 10 to 60 parts Surfactant ────── ─ 1 to 20 parts [Granule] Compound of the present invention ─────── 0.1 to 10 parts Solid carrier ─────── 90 to 99.99 parts Others ──────── 1 to 5 parts

[Formulation Example 1] Wettable powder Compound of the present invention No. 1 ──────── 50 parts Sieglite PFP ──────── 43 parts (Kaolin clay: Sieglite Industrial Co., Ltd. product name) Solpol 5050 ───────── 2 parts ( Anionic surfactant: trade name of Toho Chemical Industry Co., Ltd. Lunox 1000 C ──────── 3 parts (Anionic surfactant: trade name of Toho Chemical Industry Co., Ltd.) Carplex # 80 Anti-caking agent-2 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) The above is uniformly mixed and ground to obtain a wettable powder.

[Formulation Example 2] Emulsion Compound of the present invention No. 3 ─────── 3 parts Xylene ───────── 76 parts Isophorone ───────── 15 parts Sorpol 3005X ──────── 6 parts (Nonionic surfactant Mixture of agent and anionic surfactant: trade name of Toho Chemical Industry Co., Ltd. The above is uniformly mixed to form an emulsion.

[Formulation Example 3] Flowable agent Compound of the present invention No. 1 ──────── 35 parts Agrisol S-711 ──────── 8 parts (Nonionic surfactant: Kao Corporation trade name) Lunox 1000 C ───────── 0.5 part (anionic surfactant: Toho Chemical Industry Co., Ltd. product name) 1% Rhodopol water ───────── 20 parts (Thickener: Lone-Poulan product name) Ethylene glycol (antifreeze agent) ) ─8 parts water ──────── 28.5 parts Mix evenly to make a flowable agent.

[Formulation Example 4] Granular wettable powder (dry flowable agent) Compound of the present invention No. 3──────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────────── 5 parts (anionic surfactant: Sanyo Kokusaku Pulp Co., Ltd. trade name) Carplex # 80 ───────── 10 parts (white carbon: Shionogi Seiyaku Co., Ltd. trade name) Finely pulverize to make a dry flowable agent.

[Formulation Example 5] Granules Compound of the present invention No. 3 ────── 0.1 parts Bentonite ─────── 55.0 parts Talc ─────── 44.9 parts After uniformly mixing and pulverizing the above, add a small amount of water and knead with stirring and kneading. Granulate with an extrusion granulator and dry to give granules.

In use, the above-mentioned wettable powder, emulsion, flowable powder and granular wettable powder are diluted 50 to 1000 times with water and sprayed so that the active ingredient is 0.0001 to 10 kg per hectare (ha). . Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples.

[Test Example-1] Herbicidal effect test by soil treatment [0112] Sterilized diluvial soil was put in a plastic box having a length of 21 cm, a width of 13 cm, and a depth of 7 cm, and novier, green foxtail, oats, blackgrass, velvetleaf, spruce, Aobyu,
Morning glory, Scutellaria baicalensis, chickweed, corn,
Seeds of rice, soybean, cotton, wheat, and beet were sown in a suppot shape, covered with about 1.5 cm of soil, and then uniformly sprayed onto the soil surface with a small spray so that the amount of active ingredient was a predetermined ratio. As a drug solution for spraying, a formulation appropriately adjusted according to the above-mentioned formulation example and the like was diluted with water and used, and this was sprayed on the entire surface. Three weeks after spraying the chemical solution, the herbicidal effect on crops and various weeds was investigated according to the following criteria. The results are shown in Table 5-1.

Criteria 5: Complete death or 90% or more inhibition 4: 70-90% inhibition 3: 40-70% inhibition 2: 20-40% inhibition 1: 5-20% inhibition 0: 5 % Suppression or less

[Test Example 2] Herbicidal effect test by foliar treatment: A sterilized diluvial soil was put into a plastic box having a length of 21 cm, a width of 13 cm, and a depth of 7 cm, and Novier, Enochologsa, oats, blackgrass, velvetleaf, Ona fir, Aobyu,
Morning glory, Scutellaria baicalensis, chickweed, corn,
Seeds of rice, soybean, cotton, wheat, and beet were sown in a suppot shape and covered with soil for about 1.5 cm. When various plants reached the 2-3 leaf stage, the active ingredients were sprayed evenly on the foliage so that the amount of the active ingredient became a predetermined ratio. The chemical solution for spraying is
The wettable powder of the above formulation example was diluted with water and sprayed on the entire foliage of various plants with a small spray. The herbicidal effect on crops and various weeds was investigated 3 weeks after spraying with the chemical solution according to the criteria of Test Example-1. The results are shown in Table 5-2.

The symbols in each table have the following meanings. A (Nobie), B (Enocologsa), C (Oat grass), D (Black grass), E (Ichibi), F (Onamimi), G (Aoyuyu), H (Morning glory), I (Otoinoguri), J (Chickweed) , A (corn), b
(Rice), c (soybean), d (cotton), e (wheat),
f (beat)

[0116]

[Table 18] [Table 5-1] Herbicidal effect of soil treatment ───────────────────────────── Compound dose ABCDEFGHIJabcdef No (Kg / ha) ───────────────────────────── 1 0.63 4535115455000005 3 0.63 4523105252000000000 5 0.63 5555005155000005 6 0.63 1311105153000002 7 0.63 2312305154000003 8 0.63 4524205155000004 ──────────────────────────────

[0117]

[Table 19] [Table 5-2] Herbicidal effect of foliar treatment ───────────────────────────── Compound dose ABCDEFGHIJabcdef No . (Kg / ha) ───────────────────────────── 1 0.63 211225435355004405 3 0.63 1111333353004305 5 0.63 2123234255002303 6 0.63 1111333254003305 7 0.63 1121333254003305 8 0.63 112132435353003305 13 0.63 1211222225300200305 17 0.63 01112222154001105 ───────────────────────── ────

[Test Example 3] Herbicidal effect test by pretreatment of weeding stage under flooded condition After alluvial soil was put in a 1/5000 are Wagner pot, water was added to mix it, and a water depth of 4 cm was applied. And
After seeds of Nobie, Konagi, and Oenothera were sown in the above pot, rice seedlings at the 2.5 leaf stage were transplanted. Two pots
The plant was grown at room temperature of 0 to 30 ° C., and one day after sowing, the drug diluent was added dropwise to the water surface with a measuring pipette so that a predetermined amount was obtained. The herbicidal effect on various weeds and rice was investigated 3 weeks after the drug drop according to the criteria of Test Example-1. The results are shown in Table 6.

[0119]

[Table 20] [Table 6] Herbicidal effects in paddy fields ─────────────────────────────── Compound dose Quantum leafweed Transplanted rice No. (kg / ha) ─────────────────────────────── 1 0.16 5 5 5 5 0 3 0 .64 5 5 5 5 0 5 0.25 5 5 5 5 0 6 0.25 5 5 5 5 0 7 0.25 5 5 5 5 0 8 0.25 5 5 5 5 0 9 0.25 5 5 5 5 0 10 0.25 5 5 5 0 11 1 5 5 5 5 0 12 0.25 5 5 5 5 0 13 0.25 5 5 5 5 0 17 0.25 5 5 5 5 0 18 0.25 5 5 5 5 0 0 ──────── ───────────────────────

[0120]

INDUSTRIAL APPLICABILITY The compound of the present invention has an excellent herbicidal effect at a low dose and is useful as a herbicide for upland fields, paddy fields and non-cultivated lands.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C07D 405/14 409/14 (72) Inventor Tsutomu Namaki 1470 Shiraoka, Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama Prefecture Nissan Kagaku Kogyo Co., Ltd., Institute of Biological Sciences (72) Inventor Shigeomi Watanabe 1470 Shiraoka, Shiraoka-cho, Minami-Saitama-gun, Saitama Prefecture Nissan Kagaku Kogyo Co., Ltd., Institute of Biological Sciences (72) Inventor Kimihiro Ishikawa, Shiraoka-cho, Minami-Saitama-gun, Shiraoka 1470 Nissan Kagaku Kogyo Co., Ltd.Bioscience Research Institute (72) Inventor Yoichi Ito Shiraoka, Shiraoka-cho, Minamisaitama-gun, Saitama 1470 Nissan Kagaku Kogyo Co., Ltd.

Claims (2)

[Claims] 1. Formula (I): [In the formula, Ra represents a hydrogen atom, a halogen atom, a C _1-6 alkoxy group, a C _1-6 alkyl group or a C _1-6 haloalkyl group, and Rb is a phenyl group which may be optionally substituted with a substituent. , A benzyl group, a pyridyl group, a thienyl group or a furyl group (provided that the substituent is at least one selected from a C _1-4 alkyl group, a halogen atom, a C _1-4 haloalkyl group and a C _1-4 haloalkoxy group). Z represents a nitrogen atom or CH, Rc represents SR ¹ , OR ² or N (R ³ ) R ⁴ (provided that R ¹ , R ² , R ³ and R ⁴ are each independently Hydrogen atom, C _1-6 alkyl group, C _1-6 alkenyl group or C
_1-6 alkynyl group is represented, and R ³ and R ⁴ may form a ring of 3 to 7 together with the nitrogen atom to which they are bound, and the ring may contain an oxygen atom, a nitrogen atom or a sulfur atom. . ). ] The pyrimidine derivative represented by these. 2. A herbicide containing the pyrimidine derivative according to claim 1.