Pyrazole compounds or salts thereof, preparation method therefor, herbicidal composition and use thereof

Abstract

Disclosed are a pyrazole compound or a salt thereof, a preparation method therefor, a herbicidal composition and use thereof. The pyrazole compound or a salt thereof has a structure as shown in formula (I): ##STR00001##
wherein, R represents ##STR00002##
wherein, R′, R″, and R′″ represent hydrogen, C1-C4 alkyl, C1-C4 halogenated alkyl, C1-C4 alkoxy or halogen, R′, R″, and R′″ may be the same or different; R.sub.1 represents C1-C3 alkyl; R.sub.2 represents hydrogen or C1-C4 alkyl; R.sub.3 represents hydrogen or C1-C6 alkyl, optionally substituted phenyl, optionally substituted pyridyl, optionally substituted alkenyl, optionally substituted alkynyl, C1-C6 alkyl carbonyl, C1-C6 alkoxyl carbonyl, C1-C6 alkyl carbonyl methyl, etc. A compound having a pyrazole structure not only has excellent herbicidal effect on barnyard grass, but also is safe to rice in post-emergence application. More surprisingly, it also has good control efficacy on barnyard grass resistant to major herbicides, such as penoxsulam, quinclorac, cyhalofop-butyl, propanil, etc.

Claims

1. A pyrazole compound of formula (I) or a salt thereof: ##STR00091## wherein, R represents ##STR00092##  wherein, R′, R″, and R′″ represent hydrogen, C1-C4 alkyl, C1-C4 halogenated alkyl, or halogen, wherein R′, R″, and R′″ are the same or different, R.sub.1 represents C1-C3 alkyl; R.sub.2 represents hydrogen or C1-C4 alkyl; and R.sub.3 represents hydrogen, C1-C6 alkyl carbonyl, C1-C6 alkoxyl carbonyl, C1-C6 alkoxyl carbonyl methyl, C1-C4 alkyl sulfonyl, phenylsulfonyl substituted by alkyl, or benzoyl.

2. A method for preparing the pyrazole compound or the salt thereof according to claim 1 comprising the following steps: (1) 2-chloro-3-bromomethyl-4-methylsulfonyl benzoic acid with the structure of ##STR00093##  is reacted with a compound of formula (II) to prepare a compound of formula (III), (2) the compound of formula (III) is reacted with a compound of formula (IV) to obtain a compound of formula (V), and (3) the compound of formula (V) is subjected to a rearrangement reaction to afford a compound of formula (I) with hydrogen as R.sub.3, wherein, the compound of formula (II) is shown as follows: ##STR00094## wherein, R′, R″, and R′″ represent hydrogen, C1-C4 alkyl, C1-C4 halogenated alkyl, or halogen, R′, R″, and R′″ are the same or different; the compound of formula (III) is shown as follows: ##STR00095## wherein, R′, R″, and R′″ represent hydrogen, C1-C4 alkyl, C1-C4 halogenated alkyl, or halogen, R′, R″, and R′″ are the same or different; the compound of formula (IV) is shown as follows: ##STR00096## wherein R.sub.1 represents C1-C3 alkyl, and R.sub.2 represents hydrogen or C1-C4 alkyl; and the compound of formula (V) is shown as follows: ##STR00097## wherein, R′, R″, and R′″ represent hydrogen, C1-C4 alkyl, C1-C4 halogenated alkyl, or halogen, R′, R″, and R′″ are the same or different, R.sub.1 represents C1-C3 alkyl, and R.sub.2 represents hydrogen or C1-C4 alkyl.

3. The method according to claim 2, wherein step (1) is conducted in the presence of a solvent and an alkali, at a reaction temperature of 0-10° C., for 1-12 hours, wherein, the solvent is acetonitrile or DMF, and the alkali is sodium hydride.

4. The method according to claim 2, wherein step (2) is conducted in the presence of a solvent and a deacid reagent, at a reaction temperature of 0-10° C., for 1-6 hours, wherein, the solvent is 1,2-dichloroethane, and the deacid reagent is triethylamine.

5. The method according to claim 2, wherein step (3) is conducted in the presence of a solvent and a catalyst, at a reaction temperature of 40-60° C., for 1-6 hours, wherein, the solvent is 1,2-dichloroethane, and the catalyst is acetone cyanohydrin.

6. The method according to claim 2, further comprises step (4): a compound of formula (I) with hydrogen as R.sub.3 is reacted with a compound of formula (VI) to obtain a compound of formula (I) with a non-hydrogen group as R.sub.3, the compound of formula (VI) is shown as follows:
Y—R.sub.3   (VI) wherein, in formula VI, R.sub.3 represents C1-C6 alkyl carbonyl, C1-C6 alkoxyl carbonyl, C1-C6 alkoxyl carbonyl methyl, C1-C4 alkyl sulfonyl, phenylsulfonyl substituted by alkyl, or benzoyl, and Y represents halogen.

7. The method according to claim 6, wherein step (4) is conducted in the presence of a solvent and a deacid reagent, at a reaction temperature of 0-20° C., for 0.5-3 hours; wherein, the solvent is acetonitrile or dichloromethane, and the deacid reagent is triethylamine or potassium carbonate.

8. A herbicidal composition, which comprises a herbicidally effective amount of at least one pyrazole compound or the salt thereof according to claim 1.

9. The herbicidal composition according to claim 8, which also comprises a preparation auxiliary.

10. A method for controlling a harmful plant, comprising a step of applying a herbicidally effective amount of the herbicidal composition according to claim 8 to the plant or an area with the harmful plant.

11. A method for controlling a harmful plant growing in a desirable crop, comprising a step of applying a herbicidally effective amount the herbicidal composition according to claim 8 to the plant or an area with the harmful plant.

12. The method according to claim 11, wherein the desirable crop is a genetically modified crop or a crop treated by a genome editing technique.

13. A method for controlling a harmful plant, which comprises a step of applying a herbicidally effective amount of at least one pyrazole compound or the salt thereof according to claim 1 to the plant or an area with the plant.

14. A method for controlling a harmful plant growing in a desirable crop, comprising a step of applying a herbicidally effective amount of at least one pyrazole compound or the salt thereof according to claim 1 to the plant or an area with the harmful plant.

15. The method according to claim 14, wherein the desirable crop is a genetically modified crop or a crop treated by a genome editing technique.

16. A pyrazole compound or a salt thereof, ##STR00098## wherein R represent ##STR00099##  R′, R″, and R′″ represent hydrogen, methyl, fluoro methyl or chlorine, wherein, R′, R″, and R′″ are the same or different; R.sub.1 represents methyl, ethyl or isopropyl; R.sub.2 represents hydrogen, methyl, ethyl or cyclopropyl; and R.sub.3 represents hydrogen, C1-C6 alkyl carbonyl, C1-C6 alkoxyl carbonyl, C1-C6 alkoxyl carbonyl methyl, C1-C4 alkyl sulfonyl, phenylsulfonyl substituted by alkyl, or benzoyl.

17. A method for controlling a harmful plant growing in a desirable crop, comprising a step of applying a herbicidally effective amount of at least one pyrazole compound or the salt thereof according to claim 16 the plant or an area with the harmful plant.

18. A pyrazole compound or a salt thereof, wherein the compound is selected from TABLE-US-00004 (I) Serial NO. R.sub.1 R.sub.2 R.sub.3 R 01 —CH.sub.3 —CH.sub.3 —H 02 —CH.sub.3 —CH.sub.3 —H 03 —CH.sub.3 —CH.sub.3 —H 04 —CH.sub.3 —CH.sub.3 —H 05 —CH.sub.3 —CH.sub.2CH.sub.3 —H 06 —CH.sub.3 —CH.sub.2CH.sub.3 —H 07 —CH.sub.3 —H —H 08 —CH.sub.3 —H —H 09 —CH.sub.3 —H —H 10 —CH.sub.3 —H —H 11 —CH.sub.3 —H 12 —CH.sub.3 —H 13 —CH.sub.3 —H 14 —CH.sub.3 —H 15 —CH.sub.2CH.sub.3 —CH.sub.3 —H 16 —CH.sub.2CH.sub.3 —CH.sub.3 —H 17 —CH.sub.2CH.sub.3 —CH.sub.3 —H 18 —CH.sub.2CH.sub.3 —H —H 19 —CH.sub.2CH.sub.3 —H —H 20 —CH.sub.2CH.sub.3 —H —H 21 —CH.sub.2CH.sub.3 —H 22 —CH.sub.2CH.sub.3 —H 23 —CH.sub.2CH.sub.3 —H 24 —CH.sub.2CH.sub.3 —CH.sub.2CH.sub.3 —H 25 —CH.sub.2CH.sub.3 —CH.sub.2CH.sub.3 —H 26 —CH.sub.2CH.sub.3 —CH.sub.2CH.sub.3 —H 27 —H 28 —H —H 29 —CH.sub.2CH.sub.3 —H 30 —CH.sub.3 —H 31 —CH.sub.3 —CH.sub.3 32 —CH.sub.3 —CH.sub.3 33 —CH.sub.3 —CH.sub.3 34 —CH.sub.3 —CH.sub.3 35 —CH.sub.3 —CH.sub.3 36 —CH.sub.3 —CH.sub.3 39 —CH.sub.3 —CH.sub.3 40 —CH.sub.3 —CH.sub.3 41 —CH.sub.3 —CH.sub.3 —H

19. A method for controlling a harmful plant growing in a desirable crop, comprising a step of applying a herbicidally effective amount of at least one pyrazole compound or the salt thereof according to claim 18 to the plant or an area with the harmful plant.

Description

SPECIFIC MODE FOR CARRYING OUT THE INVENTION

(1) The above described content of the present invention is further explained through the following embodiments, and should not be interpreted by those skilled in the art as being limited to the embodiments: any techniques achieved on the basis of the content of the present invention should be included within the scope of the present invention. The technological parameters and production yield in the embodiments are presented without optimization.

Example 1

(2) The method for preparing compound 01 in Table 1 is explicated in the embodiment

(3) Step 1: The Synthesis of Intermediate (a)

(4) ##STR00073##

(5) 50 ml of acetonitrile was added into a 250 ml three-necked flask. The flask was placed in an ice-water bath, and the temperature was controlled at 5 to 10° C. 3.0 g (0.075 mol) of NaH was weighed and slowly added into the three-necked flask. The temperature was controlled below 10° C. Then 3 g (0.036 mol) of 4-methylpyrazole was dissolved into a little amount of acetonitrile, the solution was put into a dropping funnel and added dropwise to the system at about 0° C. The obtained mixture was stirred under the condition of ice-water bath after the addition. When the temperature of the system was stable, 10 g (0.030 mol) of 2-chloro-3-bromomethyl-4-methylsulfonylbenzoic acid was weighed and added slowly into the system in batches at a controlled temperature of no higher than 10° C. The system was stirred in the ice-water bath. The reaction was tracked by HPLC until the material was consumed completely. Acetonitrile was removed by rotary evaporation. 200 ml of water was added to the residue. HCl was added dropwise, the obtained mixture was stirred at room temperature to precipitate solid particles. The solid particles were collected by sucking filtration to obtain an off-white solid, which was intermediate (a). The intermediate was dried in a drying oven for further use.

(6) Step 2: The Synthesis of Intermediate (b)

(7) ##STR00074##

(8) 10 g (0.030 mol) of intermediate (a) was weighed and added into a 250 ml flask, then added with 50 ml of dichloroethane and a little amount of DMF as catalyst. Then 5 g (0.039 mol) of oxalyl chloride was dissolved into a little amount of dichloroethane. The solution was put into a dropping funnel, and dropped to the system at room temperature. The system was continued to agitate for about 2 hours at room temperature after the dropping to obtain the reaction solution containing intermediate (b). The reaction solution was directly used for the next reaction without any treatment.

(9) Step 3: The Synthesis of Compound 01

(10) ##STR00075##

(11) 4.0 g (0.036 mol) of 1,3-dimethyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask. 50 ml of 1,2-dichloroethane was added for dissolution. 12 g (0.12 mol) of triethylamine was weighed and added into the system. The reaction solution containing intermediate (b) (0.030 mol) was dropped into the system under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after 1 hour. The reaction solution containing intermediate (c) was obtained after the raw material was consumed completely. 3.0 g (0.030 mol) of triethylamine and 0.5 ml of acetone cyanohydrins were added into the reaction solution containing intermediate (c) with an argon protection, at a controlled temperature of 50 to 60° C., and reacted for 2 hours. HPLC was used to track the reaction. 100 ml water was added when the reaction was complete, then slowly dropped with HCl with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml of water, dried with anhydrous sodium sulfate, the organic solvent was removed by rotary evaporation to obtain 8.1 g of pale brown powder solid, i.e. compound 01. The content determined by HPLC was 93.9% and the yield was 67.8%.

(12) .sup.1H NMR data see Table 1.

(13) Examples 2-4 disclosed the synthesis of compound 02 to compound 04, respectively, the synthetic methods of which were similar to that of Example 1, hence their description was not given here.

Example 5

(14) The example disclosed the synthesis of compound 05 in Table 1.

(15) Step 1: The Synthesis of Intermediate (d)

(16) ##STR00076##

(17) 50 ml of acetonitrile was weighed and added into a 250 ml three-necked flask, and placed into an ice-water bath at a controlled temperature of 5 to 10° C. 4.4 g (0.11 mol) of NaH was weighed and slowly added into the flask at a controlled temperature of no higher than 10° C. 4.6 g (0.045 mol) of 4-chloropyrazole was weighed and dissolved with a little amount of acetonitrile, the solution was put into a dropping funnel and added dropwise when the system was cooled to about 0° C. The obtained reaction solution was kept stirring in the ice-water bath after the addition. After the temperature of the system was stable, 10 g (0.030 mol) of 2-chloro-3-bromomethyl-4-methylsulfonylbenzoic acid was weighed and added into the system in batches at a controlled temperature of no higher than 10° C. and kept stirring in the ice-water bath. The reaction was tracked with HPLC until the raw material was consumed completely. Acetonitrile was removed by rotary evaporation. 200 ml of water was added to the residue, then HCl was slowly added dropwise and stirred at room temperature to precipitate solid particles. The solid particles were collected by sucking filtration to obtain an off-white solid, i.e. intermediate (d). The intermediate was dried in a drying oven for further use.

(18) Step 2: The Synthesis of Intermediate (e)

(19) ##STR00077##

(20) 10.5 g (0.030 mol) of intermediate (d) was weighed and added into a 250 ml flask, and added with 50 ml of dichloroethane and a little amount of DMF as catalyst. Then 5 g (0.039 mol) of oxalyl chloride was weighed and dissolved into a little amount of dichloroethane. The solution was put into a dropping funnel and dropped into the system at room temperature. The system was kept stirring for about 2 hours at room temperature after the addition to obtain the reaction solution containing intermediate (e). The reaction solution was directly used for the next reaction without any treatment.

(21) Step 3: Synthesis of Compound 05

(22) ##STR00078##

(23) 4.5 g (0.036 mol) of 1-methyl-3-ethyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask, and added with 50 ml of 1,2-dichloroethane for dissolution. 12 g (0.012 mol) of triethylamine was weighed and put into the system. The reaction solution containing intermediate (e) (0.030 mol) was dropped into the system in an ice-water bath with an argon protection. The reaction was tracked with HPLC after one hour, the reaction solution containing intermediate (f) was obtained after the raw material was consumed completely. 3.0 g (0.030 mol) of triethylamine and 0.5 ml of acetone cyanohydrin were added into the reaction solution containing intermediate (f) with an argon protection, at a controlled temperature of 40 to 50° C., and reacted for 2 hours. The reaction was tracked with HPLC. 100 ml of water was added after the reaction was complete, then HCl was slowly added dropwise with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction, and the organic layer was washed for 2 times with 200 ml of water, dried with anhydrous sodium sulfate, the organic solvent was removed by rotary evaporation to obtain 6.7 g of dark brown powder solid, i.e. compound 05. The content determined by HPLC was 86.8% and the yield was 42.4%.

(24) .sup.1H NMR data see Table 1.

(25) Example 6 disclosed the synthesis of compound 6, the synthetic method of which was similar to that of Example 5, hence its description was not given here

Example 7

(26) The example disclosed the synthesis of compound 07 in Table 1.

(27) Step 1: The Synthesis of Intermediate (a)

(28) See Example 1.

(29) Step 2: The Synthesis of Intermediate (b)

(30) See Example 1.

(31) Step 3: The Synthesis of Compound 07

(32) ##STR00079##

(33) Weigh 3.2 g (0.033 mol) of 1-methyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask, and added with 50 ml of 1,2-dichloroethane for dissolution. 10 g (0.010 mol) of triethylamine was added into the system. The reaction solution (0.030 mol) containing intermediate (b) was added dropwise under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after one hour of reacting, the reaction solution containing intermediate (g) was obtained after the raw material was consumed completely. 3.0 g (0.030 mol) of triethylamine and 0.5 ml of acetone cyanohydrin were added into the reaction solution containing intermediate (g) with argon protection at a controlled temperature of 50 to 60° C. The reaction was tracked with HPLC after 2 hours. 100 ml water was added when the reaction was complete, then slowly added dropwise with HCl with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml water, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain 8.3 g of pale brown powder solid, i.e. compound 07. The content determined by HPLC was 96.5% and the yield was 72.4%.

(34) .sup.1H NMR data see Table 1.

(35) Example 8 to Example 10 disclosed the synthesis of compound 08 to compound 10 in Table 1, respectively, the synthetic methods of which were similar to that of Example 7, hence their description was not given here.

Example 11

(36) The example disclosed the synthesis of compound 11 in Table 1.

(37) Step 1: Synthesis of Intermediate (d)

(38) See Example 5.

(39) Step 2: Synthesis of Intermediate (e)

(40) See Example 5.

(41) Step 3: Synthesis of Compound 11

(42) ##STR00080##

(43) 4.6 g (0.033 mol) of 1-methyl-3-cyclopropyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask, and added with 50 ml of 1,2-dichloroethane for dissolution. 12 g (0.012 mol) of triethylamine was added into the system. The reaction solution containing intermediate (e) (0.030 mol) was dropped into the system under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after being reacted for 1 hour. The reaction solution containing intermediate (h) was obtained when the raw material were consumed completely. 3.0 g (0.030 mol) of triethylamine and 0.5 ml of acetone cyanohydrin were added into the reaction solution containing intermediate (h) with argon protection at a controlled temperature of 40 to 50° C. After reacting for 2 hours, the reaction was tracked with HPLC. 100 ml water was added when the reaction was complete, then slowly added with HCl drop by drop with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml water, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain 6.6 g of dark brown powder solid, i.e. compound 11. The content determined by HPLC was 83.1% and the yield was 56.5%.

(44) .sup.1H NMR data see Table 1.

(45) Example 12 to Example 14 disclosed the synthesis of compound 12 to compound 14 in Table 1, respectively, the synthetic methods of which were similar to that of Example 11, hence their description was not given here.

Example 15

(46) The example disclosed the synthesis of compound 15 in Table 1.

(47) Step 1: Synthesis of Intermediate (i)

(48) ##STR00081##

(49) 50 ml of acetonitrile was weighed and added into a 250 ml three-necked flask. The flask was placed in an ice-water bath for a controlled temperature of 5 to 10° C. 3.0 g (0.075 mol) of NaH was added into the flask slowly at a controlled temperature of 10° C. Then 2.4 g (0.036 mol) of pyrazole was dissolved into a little amount of acetonitrile, the obtained solution was put into a dropping funnel and added drop by drop when the temperature of the system was cooled to about 0° C. The system was kept stirring under the condition of ice-water bath after dropping. When the temperature of the system was stable, 10 g (0.030 mol) of 2-chloro-3-bromomethyl-4-methylsulfonyl benzoic acid was weighed and added slowly into the system in batches at a controlled temperature of no higher than 10° C. and stirred in the ice-water bath. The reaction was tracked with HPLC until the raw material was consumed completely. Acetonitrile was removed by rotary evaporation followed by an addition of 200 ml of water. HCl was added slowly drop by drop and stirred at room temperature to precipitate solid particles. The particle was collected by sucking filtration to obtain an off-white solid, i.e. intermediate (i). The intermediate was dried in a drying oven for further use.

(50) Step 2: Synthesis of Intermediate (j)

(51) ##STR00082##

(52) 10 g (0.030 mol) of intermediate (i) was weighed and added into a 250 ml flask, and added with 50 ml of dichloroethane. A little amount of DMF was drop into as catalyst. Then 5 g (0.039 mol) of oxalyl chloride was weighed and dissolved into a little amount of dichloroethane, the obtained solution was put into a dropping funnel, and dropped to the system at room temperature. The system was stirred for about 2 hours at room temperature after the dropping to obtain the reaction solution containing intermediate (j). The reaction solution was directly used for the next reaction without any treatment.

(53) Step 3: The Synthesis of Compound 15

(54) ##STR00083##

(55) 1.9 g (0.015 mol) of 1-methyl-3-cyclopropyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked boiling flask, and added with 50 ml of 1,2-dichloroethane for dissolution. 4.0 g (0.040 mol) of triethylamine was weighed and added into the system. The 1,2-dichloroethane solution (containing 0.010 mol (j)) containing intermediate (j) was dropped into the system under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after reacting for 1 hour. The reaction solution containing intermediate (k) was obtained after the raw material was consumed completely. 1.0 g (0.010 mol) of triethylamine and several drops of acetone cyanohydrin was added into the reaction solution containing intermediate (k) under argon protection at a controlled temperature of 50 to 60° C., and reacted for 2 hours. The reaction was tracked with HPLC. 100 ml water was added when the reaction was complete, and added with HCl drop by drop slowly with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml water, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain 3.6 g of pale brown powder solid, i.e. compound 15. The content determined by HPLC was 95.6% and the yield was 81.5%.

(56) .sup.1H NMR data see Table 1.

(57) Example 16 to Example 17 disclosed the synthesis of compound 16 to compound 17 in Table 1, respectively, the synthetic methods of which were similar to that of Example 15, hence their description was not given here.

Example 18

(58) The example disclosed the synthesis of compound 18 in Table 1.

(59) Step 1: Synthesis of Intermediate (i)

(60) See Example 15.

(61) Step 2: Synthesis of Intermediate (j)

(62) See Example 15.

(63) Step 3: Synthesis of Compound 18

(64) ##STR00084##

(65) 1.7 g (0.015 mol) of 1-ethyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask, and added with 50 ml of 1,2-dichloroethane for dissolution. 4.0 g (0.040 mol) of triethylamine was weighed and added into the system. The 1,2-dichloroethane solution (containing 0.010 mol (j)) containing intermediate (j) was dropped into the system under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after reacting for 1 hour. The reaction solution containing intermediate (I) was obtained when the raw material was consumed completely. 1.0 g (0.010 mol) of triethylamine and several drops of acetone cyanohydrin were added into the reaction solution containing intermediate (I) at a controlled temperature of 50 to 60° C. under argon protection, and reacted for 2 hours. The reaction was tracked with HPLC. 100 ml water was added when the reaction was complete, then HCl was added drop by drop slowly with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml water, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain 3.5 g of pale brown powder solid, i.e. compound 18. The content determined by HPLC was 94.9% and the yield was 81.3%.

(66) .sup.1H NMR data see Table 1.

(67) Examples 19-20 disclosed the synthesis of compound 19 to compound 20 in Table 1, respectively, the synthetic methods of which were similar to that of Example 18, hence their description was not given here.

Example 21

(68) The example disclosed the synthesis of compound 21 in Table 1.

(69) Step 1: Synthesis of Intermediate (i)

(70) See Example 15.

(71) Step 2: Synthesis of Intermediate (j)

(72) See Example 15.

(73) Step 3: Synthesis of Compound 21

(74) ##STR00085##

(75) 1.8 g (0.012 mol) of 1-methyl-3-cyclopropyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask, and added with 50 ml of 1,2-dichloroethane for dissolution. 3.0 g (0.040 mol) of triethylamine was added into the system. The 1,2-dichloroethane solution (containing 0.010 mol (j)) containing intermediate (j) was dropped into the system under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after reacting for 1 hour. The reaction solution containing intermediate (m) was obtained when the material was consumed completely. 1.0 g (0.010 mol) of triethylamine and several drops of acetone cyanohydrin were added into the reaction solution containing intermediate (m) at a controlled temperature of 50 to 60° C. with argon protection, and reacted for 2 hours. The reaction was tracked with HPLC. 100 ml water was added when the reaction was complete, and HCl was added drop by drop slowly with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml water, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain 3.9 g of pale brown powder solid, i.e. compound 21. The content determined by HPLC was 93.6% and the yield was 81.4%.

(76) .sup.1H NMR data see Table 1.

(77) Example 22 to Example 23 disclosed the synthesis of compound 22 to compound 23 in Table 1, respectively, the synthetic methods of which were similar to that of Example 21, hence their description was not given here.

Example 24

(78) The example disclosed the specific synthesis method for compound 24 in Table 1.

(79) Step 1: Synthesis of Intermediate (i)

(80) See Example 15.

(81) Step 1: Synthesis of Intermediate (j)

(82) See Example 15.

(83) Step 3: Synthesis of Compound 24

(84) ##STR00086##

(85) 1.7 g (0.012 mol) of 1,3-diethyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask, and 50 ml of 1,2-dichloroethane was added for dissolution. 3.0 g (0.030 mol) of triethylamine was weighed and added into the system. The 1,2-dichloroethane solution (containing 0.010 mol (j)) containing intermediate (j) was dropped into the system under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after reacting for 1 hour. The reaction solution containing intermediate (n) was obtained when the raw material was consumed completely. 1.0 g (0.010 mol) of triethylamine and several drops of acetone cyanohydrin were added into the reaction solution containing intermediate (n) at a controlled temperature of 50 to 60° C. under argon protection, and reacted for 2 hours. The reaction was tracked with HPLC. 100 ml water was added when the reaction was complete, followed by a slowly addition of HCl drop by drop with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml water, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain 3.9 g of pale brown powder solid, i.e., compound 24. The content determined by HPLC was 92.1% and the yield was 82.3%.

(86) .sup.1H NMR data see Table 1.

(87) Example 25 to Example 26 disclosed the synthesis of compound 25 to compound 26 in Table 1, respectively, the synthetic methods of which were similar to that of Example 24, hence their description was not given here.

Example 27

(88) The example disclosed the synthesis of compound 24 in Table 1.

(89) Step 1: Synthesis of Intermediate (i)

(90) See Example 15.

(91) Step 1: Synthesis of Intermediate (j)

(92) See Example 15.

(93) Step 3: Synthesis of Compound 27

(94) The example disclosed the synthesis of compound 27 in Table 1. Compound 27 can be synthesized via the following route:

(95) ##STR00087##

(96) 2.0 g (0.012 mol) of 1-isopropyl-3-cyclopropyl-5-pyrazol-ol was weighed and added into a 250 ml three-necked flask, and added with 50 ml of 1,2-dichloroethane for dissolution. 3.0 g (0.030 mol) of triethylamine was weighed and added into the system. The 1,2-dichloroethane solution (containing 0.010 mol (j)) containing intermediate (j) was added into the system under the condition of ice-water bath and argon protection. The reaction was tracked with HPLC after reacting for 1 hour. The reaction solution containing intermediate (o) was obtained when the raw material was consumed completely. 1.0 g (0.010 mol) of triethylamine and several drops of acetone cyanohydrin were added into the reaction solution containing intermediate (o) at a controlled temperature of 50 to 60° C. under argon protection, and reacted for 2 hours. The reaction was tracked with HPLC. 100 ml water was added when the reaction was complete followed by a slowly addition of HCl drop by drop slowly with stirring at room temperature until pH was adjusted to about 3. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 200 ml water, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain 4.0 g of pale brown powder solid, i.e. compound 27. The content determined by HPLC was 91.8% and the yield was 79.3%.

(97) .sup.1H NMR data see Table 1.

(98) Example 28 to Example 30 disclosed the synthesis of compound 28 to compound 30 in Table 1, respectively, the synthetic methods of which were similar to that of Example 27, hence their description was not given here.

Example 31

(99) The example disclosed the synthesis of compound 31 in Table 1. Compound 31 can be synthesized via the following route:

(100) ##STR00088##

(101) 2.2 g (0.005 mol) of compound 01 was weighed and added into a 100 ml flask, 15 ml of acetonitrile and 1.0 g (0.010 mol) of triethylamine were added and stirred under the condition of ice-water bath. 0.9 g (0.007 mol) ethyl chloroformate was dissolved into 10 ml of acetonitrile and put into a dropping funnel, and dropped under the condition of ice-water bath. The mixture was reacted under homoeothermic condition in an ice-water bath after the dropping. The reaction was tracked with HPLC until compound 01 was consumed completely. 100 ml of water and 100 ml of ethyl acetate were added when the reaction was complete. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 100 ml of saturated salt solution, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain a pale brown powder solid. 1.4 g faint yellow powder, i.e. compound 31, was obtained after being recrystallized in 95% ethyl alcohol. The content determined by HPLC was 92.9% and the yield was 61.8%.

(102) .sup.1H NMR data see Table 1.

Example 32

(103) The example disclosed the synthesis of compound 32 in Table 1. The compound 32 was synthesized via the following route:

(104) ##STR00089##

(105) 2.2 g (0.005 mol) of compound 01 was weighed and added into a 100 ml flask, 15 ml of acetonitrile and 1.4 g (0.010 mol) of potassium carbonate were added, and stirred under the condition of ice-water bath. 0.8 g (0.006 mol) ethanesulfonyl chloride was dissolved into 10 ml of acetonitrile and put into a dropping funnel, and dropped under the condition of ice-water bath. The mixture was reacted under homoeothermic condition in an ice-water bath after the dropping. The reaction was tracked with HPLC until compound 01 was consumed completely. 100 ml of water and 100 ml of ethyl acetate were added when the reaction was complete. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 100 ml of saturated salt solution, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain a yellow powder solid. 1.6 g faint yellow powder, i.e. compound 32, was obtained after being recrystallized in 95% ethyl alcohol. The content determined by HPLC was 95.1% and the yield was 65.3%.

(106) .sup.1H NMR data see Table 1.

Example 33

(107) The example disclosed the synthesis of compound 33 in Table 1. The compound 33 was synthesized via the following route:

(108) ##STR00090##

(109) 2.20 g (0.005 mol) of compound 04 was weighed and added into a 100 ml flask, 20 ml of acetonitrile and 1.40 g (0.010 mol) of potassium carbonate were added and stirred under the condition of ice-water bath. 0.95 g (0.005 mol) toluenesulfonyl chloride was dissolved into 10 ml of acetonitrile and put into a dropping funnel, and dropped under the condition of ice-water bath. The mixture was reacted under homoeothermic condition in an ice-water bath after the dropping. The reaction was tracked with HPLC until compound 04 was consumed completely. 100 ml of water and 100 ml of ethyl acetate were added when the reaction was complete. The aqueous layer was removed by extraction. The organic layer was washed for 2 times with 100 ml of saturated salt solution, dried with anhydrous sodium sulfate, concentrated by rotary evaporation to obtain a brown powder solid. 1.5 g light brown powder, i.e. compound 29, was obtained after being recrystallized in 95% ethyl alcohol. The content determined by HPLC was 95.5% and the yield was 48.5%.

(110) .sup.1H NMR data see Table 1.

(111) Examples 34-40 disclosed the synthesis of compound 34 to compound 40 in Table 1, respectively, the synthetic methods of which were similar to that of Example 33, hence their description was not given here.

(112) Biological Activity Evaluation:

(113) The activity level standard of harmful plant damage (i.e. growth inhibition rate) is as follows:

(114) Level 10: completely dead;

(115) Level 9: above 90% growth inhibition rate;

(116) Level 8: above 80% growth inhibition rate;

(117) Level 7: above 70% growth inhibition rate;

(118) Level 6: above 60% growth inhibition rate;

(119) Level 5: above 50% growth inhibition rate;

(120) Level 4: above 30% growth inhibition rate;

(121) Level 3: above 30% growth inhibition rate;

(122) Level 2: above 20% growth inhibition rate;

(123) Level 1: above 1-10% growth inhibition rate;

(124) Level 0: no effect

(125) The above described growth control rate is fresh weight control rate.

(126) Monocotyledonous and dicotyledonous weed seeds and main crop seeds (i.e. wheat, corn, rice, soybean, cotton, oilseed, millet and Sorghum) were put into a plastic pot loaded with soil. Then covered with 0.5-2 cm soil, the seeds were allowed to grow in good greenhouse environment. The test plants were treated at 2-3 leaf stage 2-3 weeks after sowing. The test compounds of the invention were dissolved with acetone respectively, then added with 80 tween and diluted by certain amount of water to certain concentration. The solution was sprayed to the plants with a sprayer. Then the plants were cultured for 3 weeks in the greenhouse. The experiment result of weed controlling effect after 3 weeks was listed in table 2.

(127) TABLE-US-00002 TABLE 2 experiment on weed control effect in post emergence stage Com- Flix- pound Barnyard grass Ning Jing 43 Corn Wheat weed serial 1 2 4 8 16 1 2 4 8 16 16 16 16 No. g/mu g/mu g/mu g/mu g/mu g/mu g/mu g/mu g/mu g/mu g/mu g/mu g/mu 1 4 7 8 10 10 0 0 0 1 2 0 0 10 2 6 8 10 10 10 0 0 1 2 6 1 1 10 3 4 6 8 8 9 0 0 0 0 1 0 0 10 4 3 4 5 5 7 0 0 1 1 1 0 0 10 5 2 2 4 7 8 0 0 1 1 1 0 0 10 6 6 8 9 10 10 0 0 1 2 5 0 0 10 7 2 3 3 6 6 0 0 0 0 0 0 0 10 8 2 2 4 7 8 0 0 0 0 0 0 0 10 9 2 2 3 5 5 0 0 0 0 0 0 0 10 10 2 4 4 7 8 0 0 0 0 1 0 0 10 11 2 4 4 6 7 0 0 0 0 0 0 0 10 12 2 4 6 7 8 0 0 0 0 0 0 0 10 13 2 2 2 5 7 0 0 0 0 0 0 0 10 14 8 9 10 10 10 0 0 1 2 5 1 2 10 15 6 7 9 10 10 0 0 1 1 4 1 1 10 16 2 3 4 4 6 0 0 0 0 0 0 0 10 17 2 2 2 4 5 0 0 0 0 0 0 0 10 18 8 8 10 10 10 0 0 2 2 4 0 0 10 19 2 3 3 4 4 0 0 0 0 0 0 0 10 20 3 4 6 6 8 0 0 0 0 0 0 0 10 21 6 7 9 10 10 0 0 2 3 4 0 0 10 22 2 4 6 6 10 0 0 0 0 0 0 0 10 23 2 3 5 7 8 0 0 0 0 0 0 0 10 24 2 2 3 5 5 0 0 2 2 4 0 0 10 25 2 3 4 4 5 0 0 0 0 0 0 0 10 26 2 2 4 3 5 0 0 0 0 0 0 0 10 27 7 7 9 10 10 0 0 1 2 3 0 0 10 28 2 5 6 6 10 0 0 0 0 0 0 0 10 29 2 3 5 7 8 0 0 0 0 0 0 0 10 30 2 3 5 7 7 0 0 0 0 0 0 0 10 31 3 5 6 8 9 0 0 0 0 0 0 0 10 32 5 6 5 7 8 0 0 0 0 0 0 0 10 33 4 6 5 7 8 0 0 0 0 0 0 0 10 34 4 5 5 7 8 0 0 0 0 0 0 0 10 35 3 3 4 4 5 0 0 0 0 0 0 0 10 36 2 3 4 4 5 0 0 0 0 0 0 0 10 37 0 1 1 2 2 0 0 0 0 0 0 0 2 38 0 1 1 2 2 0 0 0 0 0 0 0 2 39 4 6 5 7 8 0 0 0 0 0 0 0 10 40 3 5 5 7 8 0 0 0 0 0 0 0 10 41 4 5 6 7 7 0 0 1 1 1 0 0 10

(128) Table 2 indicates that many compounds of the present invention applied after emergence are safe to rice and have good efficacy on barnyard grass. At the same time, most compounds are also safe to corn and wheat and can be used in corn and wheat to control grass and broadleaf weeds.

(129) Transplanted rice safety evaluation and weed control effect evaluation in rice field:

(130) Rice field soil was loaded into a 1/1,000,000 ha pot. The seeds of Echinochloa, Scirpus juncoides, Bidens tripartite and Sagittaria trifolia were sowed and gently covered with soil, then left to stand still in greenhouse in the state of 0.5-1 cm of water storage. The tuber of Sagittaria trifolia was planted in the next day or 2 days later. It was kept at 3-4 cm of water storage thereafter. The weeds were treated by dripping the WP or SC water diluents prepared according to the common preparation method of the compounds of the present invention with pipette homogeneously to achieve specified effective amount when Echinochloa, Scirpus juncoides and Bidens tripartite reached 0.5 leaf stage and Sagittaria trifolia reached the time point of primary leaf stage.

(131) In addition, the rice field soil that loaded into the 1/1,000,000 ha pot was leveled to keep water storage at 3-4 cm depth. The 3 leaf stage rice (japonica rice) was transplanted at 3 cm of transplanting depth the next day. The compound of the present invention was treated by the same way after 5 days of transplantation.

(132) The fertility condition of Echinochloa, Scirpus juncoides, Bidens tripartite and Sagittaria trifolia 14 days after the treatment of the compound of the invention and the fertility condition of rice 21 days after the treatment of the compound of the invention respectively with the naked eye. Evaluate the weed control effect with 1-10 activity standard level, which was presented in table 3.

(133) TABLE-US-00003 TABLE 3 the experiment results of weed control effect in transplanted rice field (500 g a.i./ha) Compound Barnyard rushlike serial No. grass bulrush Beggartick Arrowhead Rice 1 10 10 9 8 0 2 10 10 10 10 3 3 10 10 10 8 0 4 10 10 9 9 0 5 10 10 10 10 1 13 10 9 9 9 0 15 10 9 9 8 2 18 10 9 10 10 1 28 10 10 10 8 0 31 10 10 10 9 1 33 10 10 10 10 1 35 10 10 10 9 0 39 10 10 8 6 0

(134) Note: The seeds of barnyard grass, rushlike bulrush, arrowhead and beggartick are collected from Heilongjing Province of China. Tests indicate that the weeds are resistant to common application rate of pyrazosulfuron-ethyl.

(135) At the same time, it is found after several tests that the compound of the present invention has good selectivity to many gramineae grass such as Zoysia japonica, bermuda grass, tall fescue, bluegrass, ryegrass and seashore paspalum etc, and is able to control many important grass weeds and broadleaf weeds. The compound also shows excellent selectivity and commercial value in the tests on soybean, cotton, oil sunflower, potato, orchards and vegetables in different herbicide application methods.