URACIL COMPOUND CONTAINING CARBOXYLATE FRAGMENT, PREPARATION METHOD THEREFOR, AND HERBICIDAL COMPOSITION AND USE THEREOF

Abstract

A uracil compound containing a carboxylate fragment, a preparation method therefor, and a herbicidal composition and use thereof are provided. The preparation method includes a contact reaction between a carboxylic acid compound and different substituted alcohol, halogenated, or sulfonate compound in a presence of a solvent. The uracil compound containing a carboxylate fragment provided by the present invention has better herbicidal activity compared with the prior art.

Claims

1. A uracil compound containing a carboxylate fragment, a structure of the uracil compound containing the carboxylate fragment is shown in the following a general formula (I): ##STR00481## in the general formula (I): R.sub.1 and R.sub.2 are selected from hydrogen or methyl respectively; or the R.sub.1, the R.sub.2 and a carbon atom attached to the R.sub.1 and the R.sub.2 form a 3-membered carbocycle; R.sub.3 is selected from C.sub.1-3 alkoxy C.sub.1-3 alkyl, C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, C.sub.2-6 alkenoxy C.sub.1-3 alkyl, C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, C.sub.2-6 alkynoxy C.sub.1-3 alkyl, C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, C.sub.1-3 alkyl S(O).sub.n C.sub.1-3 alkyl, C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or C.sub.3-9 oxygen-containing cycloalkyl; n=0, 1, or 2; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, a chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either an R configuration or an S configuration, or a mixture of the R configuration and the S configuration; and in the mixture, a ratio of the R configuration to the S configuration is 1:99 to 99:1.

2. The uracil compound containing the carboxylate fragment according to claim 1, wherein the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; or the R.sub.1, the R.sub.2, and the carbon atom attached to the R.sub.1 and the R.sub.2 form the 3-membered carbocycle; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

3. The uracil compound containing the carboxylate fragment according to claim 1, wherein the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

4. A method for preparing the uracil compound containing the carboxylate fragment according to claim 1, wherein the method comprises a contact reaction between a carboxylic acid compound shown in a formula (II) and different substituted alcohol, halogenated, or sulfonate compounds in a presence of a solvent, ##STR00482## wherein in the general formulas (I) and (II), definitions of the R.sub.1, the R.sub.2, and the R.sub.3 are same as the R.sub.1, the R.sub.2, and the R.sub.3 in claim 1.

5. The method according to claim 4, wherein a reaction temperature is 0-160 C.

6. The method according to claim 4, wherein a reaction time is 2-15 h.

7. The method according to claim 4, wherein the solvent is selected from at least one of dichloromethane, 1,2-dichloroethane, tetrahydrofuran, acetonitrile, 1,4-dioxane, toluene, o-xylene, m-xylene, p-xylene, n-heptane, n-octane, and n-nonane.

8. The method according to claim 4, wherein a molar ratio of the carboxylic acid compound shown in the formula (II) to the different substituted alcohol, halogenated, or sulfonate compounds is 1:(1-4).

9. A use of the uracil compound containing the carboxylate fragment according to claim 1 in prevention and control of weeds.

10. A composition, comprising the uracil compound containing the carboxylate fragment according to claim 1 as an active ingredient, wherein a weight percentage content of the active ingredient in the composition is 0.1-99.9%.

11. The method according to claim 4, wherein in the uracil compound containing the carboxylate fragment, the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; or the R.sub.1, the R.sub.2, and the carbon atom attached to the R.sub.1 and the R.sub.2 form the 3-membered carbocycle; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

12. The method according to claim 4, wherein in the uracil compound containing the carboxylate fragment, the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

13. The use according to claim 9, wherein in the uracil compound containing the carboxylate fragment, the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; or the R.sub.1, the R.sub.2, and the carbon atom attached to the R.sub.1 and the R.sub.2 form the 3-membered carbocycle; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

14. The use according to claim 9, wherein in the uracil compound containing the carboxylate fragment, the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

15. The composition according to claim 10, wherein in the uracil compound containing the carboxylate fragment, the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; or the R.sub.1, the R.sub.2, and the carbon atom attached to the R.sub.1 and the R.sub.2 form the 3-membered carbocycle; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

16. The composition according to claim 10, wherein in the uracil compound containing the carboxylate fragment, the R.sub.1 and the R.sub.2 are selected from the hydrogen or the methyl respectively; R.sub.3 is selected from the C.sub.1-3 alkoxy C.sub.1-3 alkyl, the C.sub.1-3 haloalkoxy C.sub.1-3 alkyl, the C.sub.2-6 alkenoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkenoxy C.sub.1-3 alkyl, the C.sub.2-6 alkynoxy C.sub.1-3 alkyl, the C.sub.2-6 haloalkynoxy C.sub.1-3 alkyl, the C.sub.3-6 oxygen-containing cycloalkyl C.sub.1-3 alkyl, or the C.sub.3-9 oxygen-containing cycloalkyl; and when the R.sub.1 is selected from the hydrogen and the R.sub.2 is selected from the methyl, the chiral carbon atom connected to the R.sub.1 and the R.sub.2 is selected from either the R configuration or the S configuration, or the mixture of the R configuration and the S configuration; and in the mixture, the ratio of the R configuration to the S configuration is 1:99 to 99:1.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0059] The present invention will be described below in conjunction with examples, but is not limited thereto. In the art, any simple replacement or improvement made by a technician to the present invention falls into the technical solution protected by the present invention.

Example 1: Preparation of Intermediate 1-8

[0060] Step 1: Preparation of Intermediate 1-1

##STR00419##

[0061] 20 g of 2-chloro-4-fluorobenzoic acid and 100 g of ethanol were put into a 500 mL four-necked flask, stirred, and cooled to 0 C., and 17.73 g of sulfoxide chloride was slowly added dropwise, where the temperature was maintained below 0 C. throughout the process. After the sulfoxide chloride was added, the solution was heated to 75 C. and stirred under reflux and reacted overnight, and the reaction solution was spun off to obtain 23.01 g of intermediate 1-1.

[0062] Step 2: Preparation of Intermediate 1-2

##STR00420##

[0063] 67.46 g of intermediate 1-1 and 337.3 g of 1,2-dichloroethane were added to a 1 L four-necked flask and cooled to 0 C., 42.09 g of fuming nitric acid (90%) and 60.12 g of sulfuric acid (98%) were slowly added dropwise, then the solution was slowly heated to room temperature and stirred until the reaction was completed, the reaction solution was transferred to a separating funnel and stood until delamination, an organic phase was taken, an inorganic phase was extracted with 1,2-di chloroethane, the acid in the organic phase was eluted with ice water until the pH value of the aqueous phase was about 7.0, and the solvent was spun off to obtain 89.81 g of crude product. 5 times the mass of n-hexane was added, recrystallization and filtration were carried out, and filter cakes were dried to obtain 42.45 g of intermediate 1-2.

[0064] Step 3: Preparation of Intermediate 1-3

##STR00421##

[0065] 60.84 g of intermediate 1-2, 4.87 g of Pt/C (5%), and 300 mL of ethanol were added into a 1 L autoclave, hydrogen pressure was controlled to 2 MPa, a reaction occurred at 45 C. for 11 hours, then the Pt/C was removed by filtration, and the filtrate was spun off to obtain 52.48 g of crude intermediate 1-3.

[0066] Step 4: Preparation of Intermediate 1-4

##STR00422##

[0067] 52.48 g of crude intermediate 24.78 g of pyridine, and 262.4 g of dichloromethane were added to a 500 mL four-necked flask and stirred at room temperature, and 34.02 g of ethyl chloroformate was weighed after 5 minutes, diluted with 68.04 g of dichloromethane, and then slowly added dropwise within 1 hour. After reaction for 5 hours, the pH value was adjusted to be weakly acidic, water was added, extraction was carried out with dichloromethane, and the organic phase was spun off to obtain 69.62 g of crude intermediate 1-4.

[0068] Step 5: Preparation of Intermediate 1-5

##STR00423##

[0069] 12.98 g of sodium ethanol was dissolved in 38 g of DMF, stirred, and cooled to 5 C. in an ice bath. A DMF (28 g) solution of ethyl 3-amino-4,4,4-trifluorocrotonate (27.95 g) was added dropwise in the ice bath. Then, a DMF solution of 36.84 g of intel mediate 1-4 was added dropwise, and the solution was heated to 100 C. and stirred for 5 h. After the reaction was completed, the pH value was adjusted to be acidic, extraction was carried out with ethyl acetate, the organic phase was washed with saturated salt water and dried with anhydrous sodium sulfate, the solvent was spun off to obtain 50 g of crude product, and the crude product was purified by column chromatography to obtain 19.05 g of intermediate 1-5.

[0070] Step 6: Preparation of Intermediate 1-6

##STR00424##

[0071] 19.05 g of intermediate 1-5 and 8.287 g of anhydrous potassium carbonate were added to a single-necked flask and dissolved with 60 g of THF, and 7.566 g of dimethyl sulfate was added, followed by stirring overnight at room temperature. After the reaction was completed, the THF was spun off, extraction was carried out with ethyl acetate, the anhydrous sodium sulfate was dried, and the organic phase was spun off to obtain 19.62 g of crude intermediate 1-6.

[0072] Step 7: Preparation of Intermediate 1-7

##STR00425##

[0073] 19.62 g of intermediate 1-6 was dissolved in 150 mL of glacial acetic acid at room temperature, the same volume of 36% hydrochloric acid was added, and a reflux reaction occurred for 8 h. After the reaction was completed, the excess solvent was evaporated under reduced pressure, and water was added to the residue to precipitate solid, followed by stirring and filtration. Filter cakes were washed with water three times, and dried at 60 C. to obtain 12.73 g of crude intermediate 1-7.

[0074] Step 8: Preparation of Intermediate 1-8

##STR00426##

[0075] 6.8 g of intermediate 1-7, 35 g of 1,2-dichloroethane, 1 drop of DMF, and 3.316 g of dichlorosulfoxide were added to a 100 ml single-necked flask and subjected to a reflux reaction for 3 h. After the reaction was completed, the excess dichlorosulfoxide and solvent were spun off to obtain 6.22 g of crude intermediate 1-8.

Example 2: Preparation of Compound 3

[0076] Step 1: Preparation of Intermediate 3-1

##STR00427##

[0077] The intermediate 1-8 (1 g) described in Example 1 and 320 mg of methyl glycolate were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 394 mg of triethylamine was added dropwise, and then a reaction occurred at room temperature for 2 h After the reaction was completed, column chromatography purification was carried out to obtain 1.02 g of intermediate 3-1.

[0078] Step 2: Preparation of Intermediate 3-2

##STR00428##

[0079] 1.02 g of intermediate 3-1, 6.12 g of hydrochloric acid (36%), and 6.12 g of acetic acid were added to a reaction flask and refluxed for 40 min, and the reaction solution was spun off to obtain 1.01 g of intermediate 3-2.

[0080] Step 3: Preparation of Intermediate 3-3

##STR00429##

[0081] 1.01 g of intermediate 3-2, 340 mg of dichlorosulfoxide, 2 drops of DMF, and 5.5 g of dichloroethane were added to a reaction flask, a reflux reaction occurred for 3 h, and the reaction solution was spun off to obtain 1.02 g of intermediate 3-3.

[0082] Step 4: Preparation of Compound 3

##STR00430##

[0083] 103.29 mg of 2-methoxyethanol and 228.95 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 3 mL of dichloromethane solution of the intermediate 3-3 (0.50 g) prepared in the last step was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 165 mg of compound 3. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.16 (d, J=7.8 Hz, 1H), 7.95 (d, J=9.6 Hz, 1H), 6.62 (s, 1H), 4.99 (s, 2H), 4.30-4.23 (m, 2H), 3.59-3.52 (m, 2H), 3.42 (s, 3H), 3.26 (s, 3H). LCMS (ESI) [M+H].sup.+=483.05, Found=482.61.

Example 3: Preparation of Compound 10

[0084] Step 1: Preparation of Compound 10

##STR00431##

[0085] 99.83 mg of 2-allyloxyethanol and 123.60 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 2.5 mL of dichloromethane solution of the intermediate 3-3 (0.40 g) described in Example 2 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 260 mg of light yellow oil as compound NMR (400 MHz, DMSO-d.sub.6) 8.16 (d, J=7.7 Hz, 1H), 7.94 (d, J=9.6 Hz, 1H), 6.61 (s, 1H), 5.93-5.7 (m, 1H), 5.24 (dq, J=17.4, 1.8 Hz, 1H), 5.13 (dt, J=10.1, 1.6 Hz, 1H), 4.99 (s, 2H), 4.27 (dd, J=5.6, 3.6 Hz, 2H), 3.96 (dt, J=5.4, 1.6 Hz, 2H), 3.67-3.55 (m, 2H). LCMS (ESI) [M+H].sup.+=509.07, Found=508.62.

Example 4: Preparation of Compound 28

[0086] Step 1: Preparation of Compound 28

##STR00432##

[0087] 20 mg of propynol ethoxylate and 148.82 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 3 nth of dichloromethane solution of the intermediate 3-3 (0.50 g) described in Example 2 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 110 mg of light yellow oil as compound 28. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.15 (d, J=7.7 Hz, 1H), 7.94 (d, J=9.6 Hz, 1H), 6.61 (s, 1H), 4.98 (s, 2H), 4.27 (dd, J=5.7, 3.4 Hz, 2H), 4.16 (d, J=2.4 Hz, 2H), 3.75-3.63 (m, 2H), 3.43 (d, J=11.5 Hz, 4H). LCMS (ESI) [M+H].sup.+=507.05, Found=506.83.

Example 5: Preparation of Intermediate 54-3

[0088] Step 1: Preparation of Intermediate 54-1

##STR00433##

[0089] 20 g of the intermediate 1-8 described in Example 1, 4.86 g of methyl D-lactate, and 100 g of dichloromethane were added to a reaction flask, blown with nitrogen, and stirred at room temperature. 5.9 g of triethylamine was added dropwise within 60 min, followed by stirring overnight at room temperature. After the reaction was completed, column chromatography purification was carried out to obtain 16 g of intermediate 54-1.

[0090] Step 2: Preparation of Intermediate 54-2

##STR00434##

[0091] 15 g of intermediate 54-1, 90 g of hydrochloric acid (36%), and 90 g of acetic acid were added into a reaction flask and stirred at 60 C. for 40 min until the reaction ended, and the solvent was spun off to obtain 14 g of intermediate 54-2.

[0092] Step 3: Preparation of Intermediate 54-3

##STR00435##

[0093] 5.0 g of intermediate 54-2, 1.63 g of sulfoxide chloride, 25 g of 1,2-dichloroethane, and 2 drops of DMF were added into a reaction flask for reflux stirring at 90 C. After one hour of reaction, the solvent was spun off to obtain 5.1 g of intermediate 54-3.

Example 6: Preparation of Compound 54

[0094] ##STR00436##

[0095] 0.6 g of the intermediate 54-3 described in Example 5, 0.120 g of 2-n ethoxyethanol, 10 g of dichloromethane, and 0.2 g of triethylamine were added to a reaction flask, blown with nitrogen, and stirred at room temperature for 1 h until the reaction ended. After the reaction was completed, column chromatography purification was carried out to obtain 0,350 g of compound 54. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (dd, J=7.7, 2.0 Hz, 1H), 7.40 (d, J=9.2 Hz, 1H), 6.37 (s, 1H), 5.36 (q, J=7.0 Hz, 1H), 4.32 (s, 2H), 3.60 (t, J=4.6 Hz, 2H), 3.57 (s, 3H), 3.36 (s, 3H), 1.62 (d, J=7.1 Hz, 3H). LCMS (ESI) [M+H].sup.+=497.07, Found=497.16.

Example 7: Preparation of Compound 61

[0096] Step 1: Preparation of Compound 61

##STR00437##

[0097] 290 mg of 2-allyloxyethanol and 330 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 10 ML of dichloromethane solution of the intermediate 54-3 (1.0 g) described in Example 5 was added dropwise, and then a reaction occurred at room temperature for 1 h. After the reaction was completed, column chromatography purification was carried out to obtain 800 mg of compound 61. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.14 (d, J=7.8 Hz, 111), 7.94 (d, J===9.6 Hz, 1H), 6.62 (d, J=3.0 Hz, 1H) (ddtd, J=16.9, 10.6, 5.3, 1.1 Hz, 1H), 5.31 (qt, J=6.5, 3.3 Hz, 1H), 5.26-5.20 (m, 1H), 5.12 (dq, J=10.4, 1.6 Hz, 1H), 4.34-4.20 (m, 2H), 3.95 (dt, J=5.3, L5 Hz, 2H), 3.60 (ddd, J=6.0, 4.2, 1.4 Hz, 2H), 3.45-3.40 (m, 3H), 1.53 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=523.08, Found=522.96.

Example 8: Preparation of Compound 79

[0098] Step 1: Preparation of Compound 79

##STR00438##

[0099] 1 g of the intermediate 54-3 described in Example 5 was dissolved in 5 mL of 1,2-dichloroethane, a 1,2-dichloroethane solution of propynol ethoxylate (220 mg) was added dropwise, the solution was stirred at 20 C. for 10 minutes, and then 330 mg of triethylamine was added dropwise. After the reaction of the raw materials was completed upon LCMS test, mL of hydrochloric acid (1N) was added for washing, the solution was separated, the organic phase was dried with anhydrous sodium sulfate, and column chromatography purification was carried out to obtain 200 mg of colorless oily liquid as compound 79. .sup.1H NMR (400 MHz, Chloroform-d) 7.97 (dd, J=7.7, 2.1 Hz, 1H), 7.40 (d, J=9.2 Hz, 111), 6.38 (d, =LO Hz, 1H), 5.36 (q, J=7.1 Hz, 1H), 5.30 (s, 1H), 4.17 (dd, J=2.4, 0.7 Hz, 2H), 3.76 (dt, J=6.9, 3.0 Hz, 2H), 3.59-3.55 (m, 3H), 1.62 (dd, J=7.1, 1.0 Hz, 3H), 1.33-1.23 (m, 2H). LCMS (ESI) [M+H].sup.+=521.07, Found=521.21.

Example 9: Preparation of Compound 88

[0100] Step 1: Preparation of Compound 88

##STR00439##

[0101] 145.14 mg of 2-(methylthio)ethanol and 199.21 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 3 mL of dichloromethane solution of the intermediate 54-3 (0.60 g) described in Example 5 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 545 mg of colorless oil as compound 88. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.15 (d, J=7.8 Hz, 1H), 7.94 (d, J=9.6 Hz, 1H), 6.63 (d, =2.9 Hz, 1H), 5.32 (dd, J=7.0, 2.0 Hz, 1H), 4.39-4.21 (m, 2H), 3.42 (s, 3H), 2.83-2.66 (m, 2H), 2.11-2.07 (m, 3H), 1.55 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=512.04, Found =512.54.

Example 10: Preparation of Compound 92

[0102] Step 1: Preparation of Compound 92

##STR00440##

[0103] 250.0 mg of compound 88 and 10 mL of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 84.11 mg of m-chloroperoxybenzoic acid was added, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 177 mg of colorless oil as compound 92. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.22 (d, J=7.7 Hz, 1H), 8.01 (d, J=9.6 Hz, 1H), 6.70 (d, J=2.9 Hz, 1H), 5.45-5.35 (m, 1H), 4.66-4.42 (m, 2H), 3.49 (s, 3H), 3.29-3.02 (m, 2H), 2.73-2.62 (m, 3H), 1.61 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=529.04, Found=528.65.

Example 11: Preparation of Compound 93

[0104] Step 1: Preparation of Compound 93

##STR00441##

[0105] 97.77 mg of 2-methylsulfonyl ethanol and 99.61 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 2 mL of dichloromethane solution of the intermediate 54-3 (0.30 g) described in Example 5 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 192 mg of compound 93. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.16 (d, J=7.7 Hz, 1H), 7.94 (d, J=9.5 Hz, 1H), 6.63 (d, J=3.2 Hz, 1H), 5.44-5.28 (m, 1H), 4.57-4.41 (m, 2H), 3.55 (t, J=5.8 Hz, 2H), 3.02 (s, 3H), 1.54 (d, J=7.0 Hz, 3H). LCMS (EST) [M+H].sup.+=545.03, Found=544.58.

Example 12: Preparation of Compound 96

[0106] ##STR00442##

[0107] 0.5 g of the intermediate 53-3 described in Example 5, 5 mL of dichloromethane, 97.2 mg of (S)-glycidol, and 0.17 g of triethylamine were added to a 25 mL single-necked flask, and stirred overnight at room temperature. After the reaction was completed, 5 mL of water was added, the solution was stirred and separated to obtain an organic phase, the organic phase was dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Column chromatography purification was carried out to obtain 215 mg of compound 96. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (d, J=7.7 Hz, 1H), 7.40 (d, 0.1=9.1 Hz, 1H), 6.38 (d, J=1.1 Hz, 1H), 5.37 (q, J=7.0 Hz, 1H), 4.49 (dd, J=12.2, 3.0 Hz, 1H), 4.07-3.94 (m, 1H), 3.57 (s, 3H), 3.22 (tt, J=9.8, 4.9 Hz, 1H), 2.84 (q, J=4.4 Hz, 1H), 2.63 (dd, J=4.7, 2.6 Hz, 1H), 1.62 (t, J=9.2 Hz, 3H). LCMS (ESI) [M+H].sup.+=495.05, Found=495.05.

Example 13: Preparation of Compound 97

[0108] ##STR00443##

[0109] 0.5 g of the intermediate 53-3 described in Example 5, 5 mL of dichloromethane, 97.2 mg of (R)-glycidol, and 0.17 g of triethylamine were added to a 25 mL single-necked flask, and stirred overnight at room temperature. After the reaction was completed, 5 mL of water was added, the solution was stirred and separated to obtain an organic phase, the organic phase was dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Column chromatography purification was carried out to obtain 330 mg of compound 97. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (d, J=7.7 Hz, 1H), 7.40 (d, J=9.2 Hz, 1H), 6.37 (d, J=2.3 Hz, 1H), 5.37 (qd, J=7.1, 2.2 Hz, 1H), 4.49 (dd, J=12.2, 2.2 Hz, 1H), 4.13-3.98 (m, 1H), 3.57 (d, J=2.0 Hz, 3H), 3.20 (tt, J=5.7, 2.8 Hz, 1H), 2.84 (t, J=4.5 Hz, 1H), 2.67 (dt, J=5.6 Hz, 1H), 1.63 (d, J=7.1 Hz, 3H). LCMS (ESI) [M+H].sup.+=495.05, Found=495.30.

Example 14: Preparation of Intermediate 105-3

[0110] Step 1: Preparation of Intermediate 105-1

##STR00444##

[0111] 324.4 mg of methyl L-lactate was added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, and the intermediate 1-8 (1 g) described in Example 1 was added dropwise, followed by 394 mg of triethylamine. Then, a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 923 mg of intermediate 105-1.

[0112] Step 2: Preparation of Intermediate 105-2

##STR00445##

[0113] 923 mg of intermediate 105-1, 6.46 g of hydrochloric acid (36%), and 6.46 g of acetic acid were added to a reaction flask and refluxed for 40 min, and the reaction solution was spun off to obtain 900 mg of intermediate 105-2.

[0114] Step 3: Preparation of Intermediate 105-3

##STR00446##

[0115] 900 mg of intermediate 105-2, 366.49 mg of dichlorosulfoxide, 2 drops of DMF, and 4.5 g of 1,2-dichloroethane were added to a reaction flask, a reflux reaction occurred for 3 h, and the reaction solution was spun off to obtain 800 mg of intermediate 105-3.

Example 15: Preparation of Compound 105

[0116] ##STR00447##

[0117] 0.6 g of the intermediate 105-3 described in Example 14, 0.120 g of 2-methoxyethanol, g of dichloromethane, and 0.2 g of triethylamine were added to a reaction flask, blown with nitrogen, and stirred at room temperature for 1 h until the reaction ended. After the reaction was completed, column chromatography purification was carried out to obtain 0.40 g of compound 105. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (dd, J=7.7, 2.0 Hz, 1H), 7.40 (d, J=9.2 Hz, 1H), 6.37 (s, 1H), 5.36 (q, J=7.0 Hz, 1H), 4.32 (s, 2H), 3.60 (t, J=4.6 Hz, 2H), 3.57 (s, 3H), 3.36 (s, 3H), 1.62 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=497.07 Found=497.34.

Example 16: Preparation of Compound 112

[0118] ##STR00448##

[0119] The intermediate 105-3 (1 g) described in Example 14 was weighed into a 25 ml single-necked flask, and 10 mL of dichloromethane, 268 mg of 2-allyloxyethanol, and 330 mg of triethylamine were added, followed by stirring at room temperature for reaction. After 15 h, the reaction ended upon LCMS test. 5 mL of water was added, and the solution was stirred and separated to obtain an organic phase. The organic phase was dried, and the excess solvent was evaporated under reduced pressure. After column chromatography purification (PE:EA=4:1), 768 mg of colorless oily liquid was obtained as compound 112. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (dd, J=7.7, 1.9 Hz, 1H), 7.40 (d, J=9.2 Hz, 1H), 6.37 (s, 1H), 5.87 (ddd, J=22.7, 10.7, Hz, 1H), 5.35 (t, J=7.0 Hz, 1H), 5.27 (dd, J=17, 2, 1.5 Hz, 1H), 5.18 (d, J=10.4 Hz, 1H), 4.43-4.24 (m, 2H), 4.00 (d, J=5.4 Hz, 2H), 3.65 (t, J=4.8 Hz, 2H), 3.57 (s, 3H), 1.62 (d, J=7.1 Hz, 3H). LCMS (ESI) [M+H].sup.+=523.08, Found=523.10.

Example 17: Preparation of Compound 130

[0120] ##STR00449##

[0121] 1 g of the intermediate 105-3 described in Example 14 was dissolved in 5 mL of 1,2-dichloroethane, a 1,2-dichloroethane solution of propynol ethoxylate (220 mg) was added dropwise, the solution was stirred at 20 C. for 10 minutes, and then 330 mg of triethylamine was added dropwise. After the reaction of the raw materials was completed upon LCMS test, mL of hydrochloric acid (1N) was added for washing, the solution was separated, the organic phase was dried with anhydrous sodium sulfate, and column chromatography purification was carried out to obtain 230 mg of colorless oily liquid as compound 130. .sup.1H NMR (400 MHz, Chloroform-d) 7.97 (dd, J=7.7, 2.1 Hz, 11-1), 7.40 (d, J=9.2 Hz, 1H), 6.38 (d, J=1.0 Hz, 1H), 5.36 (q, J=7.1 Hz, 1H), 5.30 (s, 1H), 4.17 (dd, J=2.4, 0.7 Hz, 2H, 3.76 (dt, J=6.9, 3.0 Hz, 2H), 3.59-3.55 (m, 3H), 1.62 (dd, J=7.1, 1.0 Hz, 3H), 1.33-1.23 (m, 2H). LCMS (ESI) [M+H].sup.+=521.07, Found=521.12.

Example 18: Preparation of Compound 139

[0122] Step 1: Preparation of Compound 139

##STR00450##

[0123] 145.14 mg of 2-(methylthio)ethanol and 199.21 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 3 mL of dichloromethane solution of the intermediate 105-3 (0.60 g) described in Example 14 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 419 mg of colorless oil as compound 139. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.15 (d, J=7.8 Hz, 1H), 7.94 (d, J=9.6 Hz, 1H), 6.63 (d, J=2.9 Hz, 1H), 5.32 (dd, J=7.0, 2.0 Hz, 1H), 4.39-4.21 (m, 2H), 3.42 (s, 3H), 2.83-2.66 (m, 2H), 2.11-2.07 (m, 3H), 1.55 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=512.04, Found=512.54.

Example 19: Preparation of Compound 143

[0124] Step 1: Preparation of Compound 143

##STR00451##

[0125] 250.0 mg of the compound 139 described in Example 18 and 10 mL of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 84.11 mg of m-chloroperoxybenzoic acid was added, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 170 mg of colorless oil as compound 143. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.21 (d, J=7.7 Hz, 1H), 8.01 (d, J=9.6 Hz, 1H), 6.70 (d, J=2.8 Hz, 1H), 5.41 (qt, J=7.2, 1.6 Hz, 1H), 4.70-4.43 (m, 2H), 3.48 (s, 3H), 3.27-3.00 (m, 2H), 2.65 (d, J=2.6 Hz, 3H), 1.61 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=529.04, Found=528.65.

Example 20: Preparation of Compound 144

[0126] Step 1: Preparation of Compound 144

##STR00452##

[0127] 97.77 mg of 2-methylsulfonyl ethanol and 99.61 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 2 mL, of dichloromethane solution of the intermediate 105-3 (0.30 g) described in Example 14 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 166 mg of compound 144. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.16 (d, J=7.7 Hz, 1H), 7.94 (d, J=9.5 Hz, 1H), 6.63 (d, J=3.2 Hz, 1H), 5.43-5.32 (m, 1H), 4.57-4.41 (m, 2H), 3.55 (t, J=5.8 Hz, 2H), 3.02 (s, 3H), 1.54 (d, J=7.2 Hz, 3H). LCMS (ESI) [M+H].sup.+=545.03, Found=544.58.

Example 21: Preparation of Compound 147

[0128] ##STR00453##

[0129] 0.5 g of the intermediate 105-3 described in Example 14, 5 mL of dichloromethane, 97.2 mg of (S)-glycidol, and 0.17 g of triethylamine were added to a 25 mL single-necked flask, and stirred overnight at room temperature. After the reaction was completed, 5 mL of water was added, the solution was stirred and separated to obtain an organic phase, the organic phase was dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Column chromatography purification was carried out to obtain 215 mg of compound 147. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (d, J=7.7 Hz, 1H), 7.40 (d, J=9.1 Hz, 1H), 6.38 (d, J=1.1 Hz, 1H), 5.37 (q, J=7.0 Hz, 1H), 4.49 (dd, J=12.2, 3.0 Hz, 1H), 4.07-3.94 (m, 1H), 3.57 (s, 3H), 3.22 (tt, J=9.8, 4.9 Hz, 1H), 2.84 (q, J=4.4 Hz, 1H), 2.63 (dd, J=4.7, 2.6 Hz, 1H), 1.62 (t, J=9.2 Hz, 3H). LCMS (ESI) [M+H].sup.+=495.05, Found=495.12.

Example 22: Preparation of Compound 148

[0130] ##STR00454##

[0131] 0.5 g of the intermediate 105-3 described in Example 14, 5 mL of dichloromethane, 97.2 mg of (R)-glycidol, and 0.17 g of triethylamine were added to a 25 mL single-necked flask, and stirred overnight at room temperature. After the reaction was completed, 5 mL of water was added, the solution was stirred and separated to obtain an organic phase, the organic phase was dried with anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure. Column chromatography purification was carried out to obtain 240 mg of compound 148. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (d, J=7.7 Hz, 1H), 7.40 (d, J=9.1 Hz, 1H), 6.37 (d, J=2.2 Hz, 1H), 5.37 (dd, J=7.1, 2.1 Hz, 1H), 4.49 (dd, J=12.2, 2.3 Hz, 1H), 4.07 (ddd, J=12.2, 5.9, 2.0 Hz, 1H), 3.57 (d, J=1.9 Hz, 3H), 3.20 (tt, J=5.8, 2.8 Hz, 1H), 2.83 (t, J=4.5 Hz, 1H), 2.72-2.62 (m, 1H), 1.63 (d, J=7.1 Hz, 3H). LCMS (ESI) [M+H].sup.+=495.05, Found =495.06.

Example 23: Preparation of Intermediate 156-3

[0132] Step 1: Preparation of Intermediate 156-1

##STR00455##

[0133] 20.0 g of the intermediate 1-8 described in Example 1, 4.86 g of methyl lactate, and 100 g of dichloromethane were added to a reaction flask, blown with nitrogen, and stirred at room temperature. 5.9 g of triethylamine was added dropwise within 60 min, followed by stirring overnight at room temperature. After the reaction was completed, column chromatography purification was carried out to obtain 15.8 g of intermediate 156-1.

[0134] Step 2: Preparation of Intermediate 156-2

##STR00456##

[0135] 15.0 g of intermediate 22-1, 90 g of hydrochloric acid (36%), and 90 g of acetic acid were added into a reaction flask and stirred at 60 C. for 40 min until the reaction ended, and the solvent was spun off to obtain 13.7 g of intermediate 156-2.

[0136] Step 3: Preparation of Intermediate 156-3

##STR00457##

[0137] 900 mg of intermediate 156-2, 366.49 mg of dichlorosulfoxide, 2 drops of DMF, and 4.5 of 1,2-dichloroethane were added to a reaction flask, a reflux reaction occurred for 3 h, and the reaction solution was spun off to obtain 820 mg of intermediate 156-3.

Example 24: Preparation of Compound 156

[0138] ##STR00458##

[0139] 0.6 g of the intermediate 156-3 described in Example 23, 0.120 g of 2-methoxyethanol, g of dichloromethane, and 0.2 g of triethylamine were added to a reaction flask, blown with nitrogen, and stirred at room temperature for 1 h until the reaction ended. After the reaction was completed, column chromatography purification was carried out to obtain 0.395 g of compound 156. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (dd, J=7.7, 2.0 Hz, 1H), 7.40 (d, J=9.2 Hz, 1H), 6.37 (s, 1H), 5.36 (q, J=7.0 Hz, 1H), 4.32 (s, 2H), 3.60 (t, J=4.6 Hz, 2H), 3.57 (s, 3H), 3.36 (s, 3H), 1.62 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=497.07, Found=497.30.

Example 25: Preparation of Compound 163

[0140] ##STR00459##

[0141] With reference to the methods of Examples 7 and 16, compound 163 was prepared by using the intermediate 156-3 described in Example 23 and 2-allyloxyethanol.

Example 26: Preparation of Compound 181

[0142] ##STR00460##

[0143] With reference to the methods of Examples 8 and 17, compound 181 was prepared by using the intermediate 156-3 described in Example 23 and propynol ethoxylate. .sup.1H NMR (400 MHz, Chloroform-d) 7.97 (dd, J=7.7, 2.1 Hz, 1H), 7.40 (d, J=9.2 Hz, 1H), 6.38 (d, J=1.0 Hz, 1H), 5.36 (q, J=7.1 Hz, 1H), 5.30 (5, 1H), 4.17 (dd, J=2.4, 0.7 Hz, 2H), 3.76 (dt, J=6.9, 3.0 Hz, 2H), 3.59-3.55 (m, 3H), 1.62 (dd, J=7.1, 1.0 Hz, 3H), 1.33-1.23 (m, 2H), LCMS (ESI) [M+H].sup.+=521.07, Found=521.11.

Example 27: Preparation of Compound 190

[0144] Step 1: Preparation of Compound 190

##STR00461##

[0145] 145.14 mg of 2-(methylthio)ethanol and 199.21 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 3 mL of dichloromethane solution of the intermediate 156-3 (0.60 g) described in Example 23 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 409 mg of colorless oil as compound 190. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.15 (d, J=7.8 Hz, 1H), 7.94 (d, J=9.6 Hz, 1H), 6.63 (d, J=2.9 Hz, 1H), 5.32 (dd, J=7.0, 2.0 Hz, 1H), 4.39-4.21 (m, 2H), 3.42 (s, 3H), 2.83-2.66 (m, 2H), 2.11-2.07 (m, 3H), 1.55 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=512.04, Found=512.54.

Example 28: Preparation of Compound 194

[0146] Step 1: Preparation of Compound 194

##STR00462##

[0147] 250.0 mg of compound 190 and 10 mL of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 84.11 mg of m-chloroperoxybenzoic acid was added, and then a reaction occurred at room temperature for 2 h. After the reaction was completed, column chromatography purification was carried out to obtain 166 mg of colorless oil as compound 194. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.21 (d, J=7.7 Hz, 1H), 8.01 (d, J=9.6 Hz, 1H), 6.70 (d, J=2.8 Hz, 1H), 5.41 (qt, J=7.2, 1.6 Hz, 1H), 4.70-4.43 (m, 2H), 3.48 (s, 3H), 3.27-3.00 (m, 2H), 2.65 (d, J=2.6 Hz, 3H), 1.61 (d, J=7.0 Hz, 3H). LCMS (ESI) [M+H].sup.+=529.04, Found=528.65.

Example 29: Preparation of Compound 195

[0148] Step 1: Preparation of Compound 195

##STR00463##

[0149] 97.77 mg of 2-methylsulfonyl ethanol and 99.61 mg of triethylamine were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 2 mL of dichloromethane solution of the intel mediate 156-3 (0.30 g) described in Example 23 was added dropwise, and then a reaction occurred at room temperature for 2 h. After the reaction was completed; column chromatography purification was carried out to obtain 168 mg of compound 195, .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.16 (d, J=7.7 Hz, 1H), 7.94 (d, J=9.5 Hz, 1H), 6.63 (d, J=3.2 Hz, 1H), 5.43-5.32 (m, 1H), 4.57-4.41 (m, 2H), 3.55 (t, J=5.8 Hz, 2H), 3.02 (s, 3H), 1.54 (d, J=7.2 Hz, 3H). LCMS (ESI) [M+H].sup.+=545.03, Found=544.58.

Example 30: Preparation of Compound 198

[0150] ##STR00464##

[0151] With reference to the methods of Examples 12 and 21, compound 198 was prepared by using the intermediate 156-3 described in Example 23 and (S)-glycidol. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (d, J=7.7 Hz, 1H), 7.40 (d, J=9.1 Hz, 1H), 6.38 (d, J=1.1 Hz, 1H), 5.37 (q, J=7.0 Hz, 1H), 4.49 (dd, J=12.2, 3.0 Hz, 1H), 4.07-3.94 (m, 1H), 3.57 (s, 3H), 3.22 (tt, J=9.8, 4.9 Hz, 1H), 2.84 (q, J=4.4 Hz, 1H), 2.63 (dd, J=4.7, 2.6 Hz, 1H), 1.62 (t, J=9.2 Hz, 3H). LCMS (ESI) [M+H].sup.+=495.05, Found=495.04.

Example 31: Preparation of Compound 199

[0152] ##STR00465##

[0153] With reference to the methods of Examples 13 and 22, compound 199 was prepared by using the intermediate 156-3 described in Example 23 and (R)-glycidol. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.97 (d, J=7.7 Hz, 1H), 7.40 (d, J=9.2 Hz, 1H), 6.37 (d, J=2.3 Hz, 1H), 5.37 (qd, J=7.1, 2.2 Hz, 1H), 4.49 (dd, J=12.2, 2.2 Hz, 1H), 4.13-3.98 (m, 1H), 3.57 (d, J=2.0 Hz, 3H), 3.20 (tt, J=5.7, 2.8 Hz, 1H), 2.84 (t, J=4.5 Hz, 1H), 2.67 (dt, J=10.9, 5.6 Hz, 1H), 1.63 (d, J=7.1 Hz, 3H). LCMS (ESI) [M+H].sup.+=495.05, Found=495.20.

Example 32: Preparation of Compound 207

[0154] Step 1: Preparation of Intermediate 207-1

##STR00466##

[0155] 2.36 g of methyl 2-hydroxyisobutyrate, 1.91 g of DMAP, and 50 g of dichloromethane were added to a reaction flask, blown with nitrogen, and stirred at room temperature. 5 g of the intermediate 1-8 described in Example 1 was added dropwise within 20 min, followed by stirring at room temperature for 1 h. After the reaction was completed, column chromatography purification was carried out to obtain 3.57 g of intermediate 207-1.

[0156] Step 2: Preparation of Intermediate 207-2

##STR00467##

[0157] 3.57 g of intermediate 207-1, 20 g of hydrochloric acid (36%), and 20 g of acetic acid were added into a reaction flask and stirred at 120 C. for 2 h. After a reaction ended, the reaction solution was poured into 100 ml of ice water, extraction was carried out with EA, and the organic phase was spun off to obtain 2.78 g of intermediate 207-2.

[0158] Step 3: Preparation of Compound 207-3

##STR00468##

[0159] 2.78 g of intermediate 207-2, 1.1 g of sulfoxide chloride, 30 g of 1,2-dichloroethane, and 2 drops of DMF were added into a reaction flask for reflux stirring at 90 C. After one hour of reaction, the solvent was spun off to obtain 3.2 g of intermediate 207-3.

[0160] Step 4: Preparation of Compound 207

##STR00469##

[0161] 0.3 g of intermediate 207-3, 0.054 g of 2-methoxyethanol, 10 g of dichloromethane, and g of triethylamine were added into a reaction flask, blown with nitrogen, and stirred at room temperature. After the reaction was completed, 5 mL, of water was added, and the solution was stirred and separated to obtain an organic phase. The organic phase was dried, and the excess solvent was evaporated under reduced pressure. Column chromatography purification was carried out to obtain 120 mg of white solid as compound 207. .sup.1H NMR (400 MHz, CDCl.sub.3) 7.86 (d, J=7.7 Hz, 1H), 7.38 (d, J=9.2 Hz, 1H), 6.38 (s, 1H), 4.50-4.18 (m, 2H), 3.59 (s, 2H), 3.57 (s, 3H), 3.32 (s, 3H), 1.69 (s, 6H). LCMS (ESI) [M+H].sup.+=511.08, Found=511.12.

Example 33: Preparation of Compound 214

[0162] Step 1: Preparation of Compound 214

##STR00470##

[0163] 1.04 g of 2-allyloxyethanol, 1.24 g of DMAP, and 30 g of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 20 mL of dichloromethane solution of the intermediate 207-3 (3.2 g) described in Example 32 was added dropwise, and then a reaction occurred at room temperature for 1 h. After the reaction was completed, column chromatography purification was carried out to obtain 600 mg of compound 214. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.07 (d, J=7.8 Hz, 1H), 7.92 (d, J=9.6 Hz, 1H), 6.63 (s, 1H), 5.90-5.73 (m, 1H), 5.25-5.08 (m, 2H), 4.27-4.19 (m, 2H), 3.91 (dt, J=5.3, 1.6 Hz, 2H), 3.59-3.55 (m, 2H), 3.42 (d, J=1.3 Hz, 3H), 1.63 (s, 6H). LCMS (ESI) [M+H].sup.+=537.10, Found=536.98.

Example 34: Preparation of Compound 249

[0164] ##STR00471##

[0165] 0.71 g of (S)-glycidol, 0.5 g of DMAP, 2 g of triethylamine, and 2 mL of dichloromethane were added to a reaction flask, cooled in an ice bath, and blown with nitrogen. 2.57 g of the intermediate 207-3 described in Example 32 was added dropwise to dissolve in 20 mL of dichloromethane solution, and a reaction occurred at room temperature for 3 h. After the reaction was completed, column chromatography purification was carried out to obtain 3 g of oily compound as compound 249. .sup.1H NMR (400 MHz, Chloroform-d) 7.87 (d, J=7.6 Hz, 1H), 7.39 (d, J=9.1 Hz, 1H), 6.38 (s, 1H), 4.45 (dd, J=12.2, 3.4 Hz, 1H), 4.04 (dd, J=12.2, 6.0 Hz, 1H), 3.57 (s, 3H), 3.21 (dq, J=6.4, 3.3 Hz, 1H), 2.83 (t, J=4.5 Hz, 1H), 2.64 (dd, J=4.9, 2.6 Hz, 1H), 1.70 (s, 6H). LCMS (ESI) [M+H].sup.+=509.07, Found=508.93.

Example 35: Preparation of Compound 250

[0166] ##STR00472##

[0167] 0.71 g of (R)-glycidol, 0.5 g of DMAP, 2 g of triethylamine, and 2 mL of dichloromethane were added to a reaction flask, cooled in an ice bath, and blown with nitrogen. 20 mL of dichloromethane solution of 2.57 g of the intermediate 207-3 described in Example 32 was added dropwise, and a reaction occurred at room temperature for 3 h. After the reaction was completed, column chromatography purification was carried out to obtain 2.9 g of oily compound as compound 250. .sup.1H NMR (400 MHz, Chloroform-d) 7.87 (d, J=7.7 Hz, 1H), 7.39 (d, J=9.2 Hz, 1H), 6.38 (s, 1H), 4.44 (dd, J=12.2, 3.4 Hz, 1H), 4.04 (dd, J=12.2, 6.0 Hz, 1H), 3.56 (s, 3H), 3.20 (dq, J=6.1, 3.5 Hz, 1H), 2.82 (t, J=4.5 Hz, 1H), 2.63 (dd, J=4.8, 2.6 Hz, 1H), 1.70 (s, 6H). LCMS (ESI) [M+H].sup.+=509.07, Found=509.10.

Example 36: Preparation of Compound 251

[0168] Step 1: Preparation of Compound 251

##STR00473##

[0169] With reference to the methods of Examples 34 and 35, compound 251 was prepared by using the intermediate 207-3 described in Example 32 and glycidol. .sup.1H NMR (400 MHz, Chloroform-d) 7.87 (d, J=7.6 Hz, 1H), 7.39 (d, J=9.1 Hz, 1H), 6.38 (s, 1H), 4.45 (dd, J=12.2, 3.4 Hz, 1H), 4.04 (dd, J=12.2, 6.0 Hz, 1H), 3.57 (s, 3H), 3.21 (dq, J=6.4, 3.3 Hz, 1H), 2.83 (t, J=4.5 Hz, 1H), 2.64 (dd, J=4.9, 2.6 Hz, 1H), 1.70 (s, 6H). LCMS (ESI) [M+H].sup.+=509.07, Found=508.97.

Example 37: Preparation of Compound 258

[0170] Step 1: Preparation of Compound 258-1

##STR00474##

[0171] 0.6 g of methyl 1-hydroxy-1-cyclopropanecarboxylate, 0.57 g of DMAP, and 25 g of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 10 mL of dichloromethane solution of the intermediate 1-8 (1.22 g) described in Example 1 was added dropwise, and then a reaction occurred at room temperature for 1 h. After the reaction was completed, column chromatography purification was carried out to obtain 1.1 g of intermediate 258-1.

[0172] Step 2: Preparation of Compound 258-2

##STR00475##

[0173] 1.1 g of intermediate 258-1, 8 g of hydrochloric acid (36%), and 8 g of acetic acid were added into a reaction flask and stirred at 110 C. for 4 h. After a reaction ended, the reaction solution was poured into 100 ml of ice water, extraction was carried out with EA, and the organic phase was spun off to obtain 1.06 g of intermediate 258-2.

[0174] Step 3: Preparation of Compound 258-3

##STR00476##

[0175] 1.06 g of intermediate 258-2, 0.42 g of sulfoxide chloride, 20 g of 1,2-dichloroethane, and 2 drops of DMF were added into a reaction flask for reflux stirring at 90 C. After one hour of reaction, the solvent was spun off to obtain 1.1 g of intermediate 258-3.

[0176] Step 4: Preparation of Compound 258

##STR00477##

[0177] 0.211 g of 2-methoxyethanol, 0.323 g of triethylamine, and 15 g of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 10 mL of di chloromethane solution of the intermediate 258-3 (1.0 g) was added dropwise, and then a reaction occurred at room temperature for 1 h. After the reaction was completed, column chromatography purification was carried out to obtain 201 mg of compound 258. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.21 (d, J=7.6 Hz, 1H), 8.01 (d, J=9.4 Hz, 1H), 6.70 (s, 1H), 4.29 (t, J=4.7 Hz, 2H), 3.57 (t, J=4.6 Hz, 2H), 3.49 (s, 3H), 3.29 (s, 3H), 1.67-1.48 (m, 4H). LCMS (ESI) [M+H].sup.+=509.07, Found=508.92.

Example 38: Preparation of Compound 300

[0178] Step 1: Preparation of Compound 300

##STR00478##

[0179] 0.308 g of (S)-glycidol, 0.485 g of triethylamine, and 20 g of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 15 mL of dichloromethane solution of the intermediate 258-3 (1.5 g) described in Example 37 was added dropwise, and then a reaction occurred at room temperature for 1 h. After the reaction was completed, column chromatography purification was carried out to obtain 212 mg of compound 300. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.22 (d, J=7.8 Hz, 1H), 8.01 (d, J=9.6 Hz, 1H), 6.69 (s, 1H), 4.52 (dd, J=12.3, 2.6 Hz, 1H), 4.03 (dd, J=12.3, 6.3 Hz, 1H), 3.51-3.45 (m, 3H), 3.24 (ddt, J=6.7, 4.2, 2.6 Hz, 1H), 2.83 (dd, J=5.0, 4.2 Hz, 1H), 2.68 (dd, J=5.0, 2.6 Hz, 1H), 1.68-1.51 (m, 4H). LCMS (ESI) [M+H].sup.+=507.05, Found=506.96.

Example 39: Preparation of Compound 301

[0180] Step 1: Preparation of Compound 301

##STR00479##

[0181] 0.205 g of (R)-glycidol, 0.323 g of triethylamine, and 15 g of dichloromethane were added to a reaction flask, cooled in an ice bath, stirred, and blown with nitrogen, 15 mL of dichloromethane solution of the intermediate 258-3 (1.0 g) descried in Example 37 was added dropwise, and then a reaction occurred at room temperature for 1 h. After the reaction was completed, column chromatography purification was carried out to obtain 222 mg of compound 301. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.15 (d, J=7.8 Hz, 1H), 7.94 (d, J=9.6 Hz, 1H), 6.63 (s, 1H), 4.46 (dd, J=12.3, 2.7 Hz, 1H), 3.97 (dd, J=12.3, 6.2 Hz, 1H), 3.46-3.40 (m, 3H), 3.18 (ddt, J=6.7, 4.2, 2.6 Hz, 1H), 2.77 (dd, J=5.0, 4.3 Hz, 1H), 2.62 (dd, J=5.0, 2.6 Hz, 1H), 1.61-1.45 (m, 4H). LCMS (ESI) [M+H].sup.+=507.05, Found=507.10.

Example 40: Preparation of Compound 302

[0182] Step 1: Preparation of Compound 302

##STR00480##

[0183] With reference to the methods of Examples 38 and 39, compound 302 was prepared by using the intermediate 258-3 described in Example 37 and glycidol. .sup.1H NMR (400 MHz, DMSO-d.sub.6) 8.22 (d, J=7.8 Hz, 1H), 8.01 (d, J=9.6 Hz, 1H), 6.69 (s, 1H), 4.52 (dd, J=12.3, 2.6 Hz, 1H), 4.03 (dd, J=12.3, 6.3 Hz, 1H), 3.51-3.45 (m, 3H), 3.24 (ddt, J=6.7, 4.2, 2.6 Hz, 1H), 2.83 (dd, J=5.0, 4.2 Hz, 1H), 2.68 (dd, J=5.0, 2.6 Hz, 1H), 1.68-1.51 (m, 4H). LCMS (ESI) [M+H].sup.+=507.05, Found=506.88.

Example 41: Greenhouse Experiments

[0184] A herbicidal activity test method for the compounds of the present invention was as follows:

[0185] Seed Treatment; pre-emergence: quantitative seeds of gramineous weeds (Echinochloa crusgalli, Eleusine indica, Digitaria sanguinalis, Alopecurus japonicus, Beckmannia syzigachne, Leptochloa chinensis, Polypogon fugax, Alopecurus, aequalis, Lolium multiflorum, and Poa annua), broad-leaved weeds (Eclipta prostrata, Amaranthus retroflexus, Brassica juncea, Malachium aquaticum, Conyza canadensis, and Sesbania cannabina), and Cyperus iria were sown in plastic pots having a diameter of 7 cm and holes at the bottom and filled with nutrient soil (sandy soil, pH 6.1, organic matter 1%) respectively, the seeds were covered with an appropriate amount of soil after being sown, then the soil was wetted with water from the bottom, the seeds were cultured in a constant-temperature illuminated culture room for 24 h, and the soil was sprayed by using a 3WP-2000 traveling spray tower produced by the Nanjing Institute of Agricultural Mechanization of the Ministry of Agriculture, where a rotational speed of a main shaft was 96 mm/r, a spray height was 300 mm, an effective spraying range of a nozzle was 350 mm, a spray area was 0.35 m 2, and a flow rate at the nozzle was 390 mL/min.

[0186] Post-emergence: an appropriate quantity of seeds of gramineous weeds (Echinochloa crusgalli, Eleusine indica, Digitaria sanguinalis, Alopecurus japonicus, Beckmannia syzigachne, Leptochloa chinensis, Polypogon fugax, Alopecurus aequalis, Lolium multiflorum, and Poa annua), broad-leaved weeds (Eclipta prostrata, Amaranthus retroflexus, Brassica juncea, Malachium aquaticum, Conyza canadensis, and Sesbania cannabina), and Cyperus iria were sown in plastic pots having a diameter of 7 cm and holes at the bottom and filled with nutrient soil (sandy soil, pH 6.1, organic matter 1%) respectively, the seeds were covered with an appropriate amount of soil after being sown, then the soil was wetted with water from the bottom, the seeds were cultured in a constant-temperature illuminated culture room until a 2-4 leaf stage, and stems and leaves underwent spray treatment. After the treatment, the test materials were placed in a laboratory and cultured in the constant-temperature illuminated culture room after the liquid was naturally dry in the shade, and results were determined 21 days later.

[0187] Classification standards for prevention and control effects: [0188] A indicates that the inhibition rate was greater than or equal to 85% to 100%; [0189] B indicates that the inhibition rate was greater than or equal to 70% to less than 85%; [0190] C indicates that the inhibition rate was greater than or equal to 55% to less than 70%; [0191] D indicates that the inhibition rate was less than 55%.

[0192] The test results showed that the compounds of the general formula (I) generally had excellent prevention and control effects on various weeds at a dose of 30 g a.i./hm.sup.2, reaching class A.

[0193] According to the foregoing test method, a parallel experiment was carried out on herbicidal activities of some compounds of the general formula (I), the compound Butafenacil (compound 47 in the patent specification) specifically disclosed in U.S. Pat. No. 5,183,492A, and the compound CK (compound 1 in the patent specification) specifically disclosed in U.S. Pat. No. 5,183,492A, at application doses of 7.5 g a.i./ha and 15 g a.i./ha. Results were shown in Table 2:

TABLE-US-00002 TABLE 2 Herbicidal activities of some compounds of the general formula (I) and control compounds (post-emergence, fresh weight inhibition rate %) Number of Dose Alopecurus Polypogon Sesbania compound a.i./ha japonicus fugax cannabina 3 7.5 B B A 15 A A A 105 7.5 A B A 15 A A A 207 7.5 A A A 15 A A A 214 7.5 A A A 15 A A A 258 7.5 A A A 15 A A A Butafenacil 7.5 D D C 15 D C B CK 7.5 D D C 15 C C B

[0194] Described above are preferred embodiments of the present invention. It should be noted that, for those of ordinary skill in the art, many variations and improvements may be made without departing from the conception of the present invention, and the variations and improvements fall into the protection scope of the present invention.