A pyrrolidone-containing 2-phenylpyridine derivative, a synthetic method, application and herbicide thereof

Abstract

The application provides a pyrrolidone-containing 2-phenylpyridine derivative and a synthesis method, application and herbicide thereof, and belongs to the technical field of compound synthesis. The structural general formula of the pyrrolidone-containing 2-phenylpyridine derivative is shown in formula I or formula II. The pyrrolidone-containing 2-phenylpyridine derivative has a novel molecular skeleton, has excellent herbicidal activity on three broadleaf weeds of amaranthus retroflexus, abutilon theophrasti and medicago sativa and three gramineous weeds of euphorbia heterophylla, digitaria sanguinalis and lolium multiflorum, and has good crop selectivity on wheat, corn and rice.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of compound synthesis, and in particular to a 2-phenylpyridine derivative containing pyrrolidone and a synthesis method, application and herbicide thereof. BACKGROUND

[0002] Weeds pose a significant threat to crop yield, competing for basic resources such as water, light and nutrients, resulting in a decrease in crop productivity of nearly one-third and causing huge economic losses. Currently, chemical control is the most direct and effective method for weed management. However, the widespread use of chemical pesticides has led to several key issues, including weed resistance and environmental pollution. Therefore, there is an urgent need to develop new herbicides with high efficiency, low toxicity, low residual amount and excellent crop selectivity. To address this challenge, the use of new protoporphyrinogen IX oxidase inhibitors (PPO, EC 1.3.3.4) has become a promising strategy. Flumioxazin is a widely used commercial PPO herbicide. However, flumioxazin lacks crop selectivity, limiting its application to pre-emergence crop weed control in cotton, peanut and soybean fields, as well as integrated weed management in no-tillage fields and orchards. This limitation emphasizes the need for researchers to develop new PPO inhibitors with high herbicidal activity and good crop selectivity.

[0003] Pyrrolidone derivatives have a wide range of biological activities. Among them, pyrrolidone derivatives have excellent herbicidal activity, such as commercial herbicides such as flurazole and tetrafluronamine, which play an important role in weed management. SUMMARY

[0004] To solve the above problems, the present application provides a 2-phenylpyridine derivative containing pyrrolidone and a synthesis method, application and herbicide thereof. The 2-phenylpyridine derivative containing pyrrolidone has a novel molecular skeleton and excellent herbicidal activity against three broadleaf weeds, including amaranthus, abutilon and alfalfa, and three gramineous weeds, including barnyard grass, crabgrass and blackgrass, while having good crop selectivity for wheat, corn and rice.

[0005] To achieve the above purpose, the present application provides the following technical solutions:

[0006] The present application provides a 2-phenylpyridine derivative containing pyrrolidone, the structure of which is shown in formula I or formula II:

[0007]

[0008] wherein X is selected from oxygen, sulfur or NH;

[0009] R1is selected from the group consisting of hydrogen, phenyl, halophenyl, phenyl-Ci-C4alkyl, phenyl-Ci-C4alkoxy, 5- to 6-membered heterocycle-Ci-C6alkyl, Ci-C6alkyl, Ci-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, Ci-C6alkylcarbonyl, phenyl-Ci-C6alkylcarbonyl, Ci-C6alkoxycarbonyl, phenoxycarbonyl, phenyl-Ci-C6alkoxycarbonyl, cyano-Ci-C6alkyl, Ci-C6alkylsulfinyl-Ci-C6alkyl, Ci-C6alkylsulfonyl-Ci-C6alkyl, Ci-C6alkylcarbonyl-Ci-C6alkyl, Ci-C6alkylcarbonyloxy-Ci-C6alkyl, Ci-C6alkoxycarbonyloxy-Ci-C6alkyl, Ci-C6alkoxycarbonyl-Ci-C6alkyl, Ci-C6alkoxycarbonyl-C3-C6alkenyl, Ci-C6alkoxycarbonyl-halogenated C3-C6alkenyl, Ci-C6haloalkoxycarbonyl-Ci-C6alkyl, C3-C6alkenyloxycarbonyl-Ci-C6alkyl, C3-C6alkynyloxycarbonyl-Ci-C6alkyl, Ci-C6alkylamino-Ci-C6alkyl, Ci-C6alkylaminocarbonyl-Ci-C6alkyl and C3-C6cycloalkyl-Ci-C6alkyl;

[0010] R2is selected from the group consisting of hydrogen, phenyl, halophenyl, phenyl-Ci-C4alkyl, phenyl-Ci-C4alkoxy, 5- to 6-membered heterocycle-Ci-C6alkyl, Ci-C6alkyl, Ci-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, Ci-C6alkylcarbonyl, phenyl-Ci-C6alkylcarbonyl, Ci-C6alkoxycarbonyl, phenoxycarbonyl, phenyl-Ci-C6alkoxycarbonyl, cyano-Ci-C6alkyl, Ci-C6alkylsulfinyl-Ci-C6alkyl, Ci-C6alkylsulfonyl-Ci-C6alkyl, Ci-C6alkylcarbonyl-Ci-C6alkyl, Ci-C6alkylcarbonyloxy-Ci-C6alkyl, Ci-C6alkoxycarbonyloxy-Ci-C6alkyl, Ci-C6alkoxycarbonyl-Ci-C6alkyl, Ci-C6alkoxycarbonyl-C3-C6alkenyl, Ci-C6alkoxycarbonyl-halogenated C3-C6alkenyl, Ci-C6haloalkoxycarbonyl-Ci-C6alkyl, C3-C6alkenyloxycarbonyl-Ci-C6alkyl, C3-C6alkynyloxycarbonyl-Ci-C6alkyl, Ci-C6alkylamino-Ci-C6alkyl, Ci-C6alkylaminocarbonyl-Ci-C6alkyl and C3-C6cycloalkyl-Ci-C6alkyl.

[0011] The application also provides a synthesis method of the pyrrolidone-containing 2-phenylpyridine derivative.

[0012] 1) performing a condensation reaction of 6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione and compound 1 to obtain compound 2;

[0013] The condensation reaction is performed at a temperature of 50-80°C for 6-12 hours;

[0014] The structures of the compounds 1 and 2 are as follows:

[0015]

[0016]

[0017] 2) performing an acylation reaction of compound 2 and oxalyl chloride under catalysis of N,N-dimethylformamide to obtain compound 3;

[0018] The acylation reaction is performed at a temperature of 25-40°C for 2-6 hours;

[0019] The structure of the compound 3 is as follows:

[0020]

[0021] 3) performing a substitution reaction of compound 3 and different substituted alcohols or amines under action of triethylamine to obtain compound 4;

[0022] The substitution reaction is performed at a temperature of 25-40°C for 2-6 hours;

[0023] The structure of the compound 4 is as follows:

[0024]

[0025] Preferably, the molar ratio of the 6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione to compound 1 in step 1) is 1-5;

[0026] The solvent used in the condensation reaction includes one or more of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, tetrahydrofuran and dichloromethane;

[0027] The acyl chloride used in the acylation reaction of step 2) includes one or more of acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride and thionyl chloride;

[0028] The molar ratio of the acyl chloride to compound 2 is 1-3; the solvent used in the acylation reaction includes one or more of dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, chloroform and chlorobenzene;

[0029] The catalyst used in the acylation reaction includes one or more of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile and pyridine;

[0030] The acid-binding agent used in the step 3) substitution reaction includes one or more of pyridine, triethylamine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide and potassium hydroxide;

[0031] The molar ratio of the base to compound 3 in the substitution reaction is 1-3;

[0032] The solvent used in the substitution reaction includes one or more of dichloromethane, diethyl ether, carbon tetrachloride, toluene and benzene;

[0033] The molar ratio of the different substituted alcohol or amine to compound 3 in the substitution reaction is 1-3.

[0034] The present application also provides a synthesis method of the pyrrolidone-containing 2-phenylpyridine derivative according to the technical solution described above, when the structure general formula is formula II, the method comprises the following steps:

[0035] A. Compound 1 and 3-hydroxydihydrofuran-2(3H)-one undergo a substitution reaction under the action of trimethylaluminum to obtain compound 5;

[0036] The temperature of the substitution reaction is 0-30℃, and the time is 4-8 hours;

[0037] The structures of the compounds 1 and 5 are as follows:

[0038]

[0039] B. Compound 5 undergoes a substitution reaction under the action of triphenylphosphine and carbon tetrabromide to generate a bromide intermediate, and then reacts with 1,8-diazabicyclo[5,4,0]undec-7-ene to obtain compound 6;

[0040] The temperature of the substitution reaction is 0-30℃, and the time is 4-8 hours;

[0041] The structure of the compound 6 is as follows:

[0042]

[0043] C. Compound 6 and different substituted acyl chlorides undergo a substitution reaction under the action of triethylamine to obtain compound 7; the temperature of the substitution reaction is 25-40℃, and the time is 2-6 hours;

[0044] The structure of the compound 7 is as follows:

[0045]

[0046] Preferably, the molar ratio of 3-hydroxydihydrofuran-2(3H)-one to compound 1 in the step A is 1-3;

[0047] The molar ratio of trimethylaluminum to compound 1 is 1-3;

[0048] The molar ratio of triphenylphosphine to compound 5 in the step B is 1-3;

[0049] The molar ratio of carbon tetrabromide to compound 5 is 1-3;

[0050] The molar ratio of 1,8-diazabicyclo[5,4,0]undec-7-ene to the intermediate bromide is 1-3;

[0051] The acid binding agent used in the substitution reaction in the step C includes one or more of pyridine, triethylamine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide and potassium hydroxide;

[0052] The molar ratio of the base to compound 6 in the substitution reaction is 1-3;

[0053] The solvent used in the substitution reaction includes one or more of dichloromethane, diethyl ether, carbon tetrachloride, toluene and benzene;

[0054] The molar ratio of the different substituted acyl chloride to compound 6 in the substitution reaction is 1-3.

[0055] The application further provides application of the pyrrolidone-containing 2-phenylpyridine derivative in the above technical solution to weed control.

[0056] Preferably, the weeds include one or more of amaranthus retroflexus, abutilon theophrasti, medicago sativa, euphorbia heterophylla, digitaria sanguinalis and lolium multiflorum.

[0057] Preferably, the use amount of the pyrrolidone-containing 2-phenylpyridine derivative is 9.375-150 g ai / ha.

[0058] Preferably, the use amount of the pyrrolidone-containing 2-phenylpyridine derivative is 37.5-75 g ai / ha.

[0059] The application further provides a herbicide, characterized in that the herbicide comprises the pyrrolidone-containing 2-phenylpyridine derivative in the above technical solution.

[0060] The application has the following beneficial effects:

[0061] The pyrrolidinone-containing 2-phenylpyridine derivative provided by the present application has good herbicidal effect on weeds such as barnyardgrass, crabgrass, dogtailgrass, shepherdspurse, amaranth and abutilon. In particular, the compounds 4a, 4b, 4d, 4f, 4j, 4k, 4l, 4m, 4o, 4q, 4r, 4v and 4w have excellent herbicidal effect on amaranth, abutilon, alfalfa, barnyardgrass, crabgrass and blackgrass; the compounds 4c, 4e, 4g, 4h, 4i, 4n, 4p, 4s, 4t, 4u, 7a, 7b and 7c have excellent herbicidal effect on amaranth, abutilon and alfalfa; the compounds 7e, 7f, 7g and 7h have excellent herbicidal effect on amaranth and abutilon. The compounds 4d, 4f and 4l have particularly excellent herbicidal effect on amaranth, abutilon, alfalfa, barnyardgrass, crabgrass and blackgrass. DETAILED DESCRIPTION

[0062] The present application provides a pyrrolidinone-containing 2-phenylpyridine derivative, the structural general formula of which is shown in formula I or II:

[0063]

[0064] wherein X is selected from oxygen, sulfur or NH;

[0065] R 1 is selected from any one of hydrogen, phenyl, halophenyl, phenyl-C1-C4alkyl, phenyl-C1-C4alkoxy, 5-6 membered heterocyclic-C1-C6alkyl, C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C1-C6alkylcarbonyl, phenyl-C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl, phenoxycarbonyl, phenyl-C1-C6alkoxycarbonyl, cyano-C1-C6alkyl, C1-C6alkylsulfinyl-C1-C6alkyl, C1-C6alkylsulfonyl-C1-C6alkyl, C1-C6alkylcarbonyl-C1-C6alkyl, C1-C6alkylcarbonyloxy-C1-C6alkyl, C1-C6alkoxycarbonyloxy-C1-C6alkyl, C1-C6alkoxycarbonyl-C1-C6alkyl, C1-C6alkoxycarbonyl-C3-C6alkenyl, C1-C6alkoxycarbonyl-halogenated C3-C6alkenyl, C1-C6haloalkoxycarbonyl-C1-C6alkyl, C3-C6alkenyloxycarbonyl-C1-C6alkyl, C3-C6alkynyloxycarbonyl-C1-C6alkyl, C1-C6alkylamino-C1-C6alkyl, C1-C6alkylaminocarbonyl-C1-C6alkyl, C3-C6cycloalkyl-C1-C6alkyl;

[0066] R 2any one of hydrogen, phenyl, halophenyl, phenyl-Ci-C4alkyl, phenyl-Ci-C4alkoxy, 5- to 6-membered heterocycle-Ci-C6alkyl, Ci-C6alkyl, Ci-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, Ci-C6alkylcarbonyl, phenyl-Ci-C6alkylcarbonyl, Ci-C6alkoxycarbonyl, phenoxycarbonyl, phenyl-Ci-C6alkoxycarbonyl, cyano-Ci-C6alkyl, Ci-C6alkylsulfinyl-Ci-C6alkyl, Ci-C6alkylsulfonyl-Ci-C6alkyl, Ci-C6alkylcarbonyl-Ci-C6alkyl, Ci-C6alkylcarbonyloxy-Ci-C6alkyl, Ci-C6alkoxycarbonyloxy-Ci-C6alkyl, Ci-C6alkoxycarbonyl-Ci-C6alkyl, Ci-C6alkoxycarbonyl-C3-C6alkenyl, Ci-C6alkoxycarbonyl-halogenated C3-C6alkenyl, Ci-C6haloalkoxycarbonyl-Ci-C6alkyl, C3-C6alkenyloxycarbonyl-Ci-C6alkyl, C3-C6alkynyloxycarbonyl-Ci-C6alkyl, Ci-C6alkylamino-Ci-C6alkyl, Ci-C6alkylaminocarbonyl-Ci-C6alkyl, C3-C6cycloalkyl-Ci-C6alkyl.

[0067] In the present application, the pyrrolidinone-containing 2-phenylpyridine derivatives are prepared according to the following synthesis route:

[0068]

[0069] Reagents and conditions: (a) 6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione, CH3CN, 60°C;

[0070] (b) oxalyl chloride, DCM, DMF, r.t.; (c) R 1 NH2 or R 1 OH, Et3N, DCM, 0°C to r.t.; (d) 3-hydroxydihydrofuran-2(3H)-one, Al(CH3)3, DCM, 0°C to r.t.; (e) PPh3, CBr4, DCM, 0°C to r.t.; (f) DBU, CCl3, r.t. (g) R2OCl, Et3N, DCM.

[0071] 1) Synthesis of compound 2 from compound 1 (condensation reaction)

[0072] The synthesis of compound 2 from compound 1 is preferably a condensation reaction of compound 1 with 6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione, thereby obtaining compound 2.

[0073] As the amount of 6,6-dimethyl-5,7-dioxaspiro[2.5]octane-4,8-dione used in the above condensation reaction, 1 to 5 equivalents (mole ratio) relative to the amount of Compound 1 is preferable, and 2.5 equivalents (mole ratio) is more preferable.

[0074] As the solvent used in the above condensation reaction, one or more of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, tetrahydrofuran and dichloromethane is included, and acetonitrile is preferable as the solvent.

[0075] As the temperature of the above condensation reaction, 50 to 80°C is preferable.

[0076] As the time of the above condensation reaction, 6 to 12 hours is preferable.

[0077] 2) Synthesis method of Compound 3 from Compound 2 (acylation reaction)

[0078] The synthesis method of Compound 3 from Compound 2 is preferably that Compound 2 is subjected to an acylation reaction with oxalyl chloride under catalysis of N,N-dimethylformamide to obtain Compound 3.

[0079] As the acyl chloride used in the above acylation reaction, one or more of acetyl chloride, benzoyl chloride, oxalyl chloride, chloroacetyl chloride, trichloroacetyl chloride and sulfuryl chloride is included, and oxalyl chloride is preferable as the acylating agent.

[0080] As the amount of acyl chloride used in the above acylation reaction, 1 to 3 equivalents (mole ratio) relative to the amount of Compound 2 is preferable, and 1.5 equivalents (mole ratio) is more preferable.

[0081] As the solvent used in the above acylation reaction, one or more of dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, chloroform, chlorobenzene and the like is included, and dichloromethane is preferable as the solvent.

[0082] As the catalyst used in the above acylation reaction, one or more of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, pyridine and the like is included, and N,N-dimethylformamide is preferable as the catalyst.

[0083] As the amount of acyl chloride used in the above acylation reaction, 5 to 10% equivalents (mole ratio) relative to the amount of Compound 2 is preferable, and 5% equivalents (mole ratio) is more preferable.

[0084] As the temperature of the above acylation reaction, 25 to 40°C is preferable.

[0085] As the time of the above acylation reaction, 2 to 6 hours is preferable.

[0086] 3) Synthesis of compound 4 from compound 3 (substitution reaction)

[0087] The synthesis of compound 4 from compound 3 is preferably carried out by substitution reaction of compound 3 with different substituted alcohols or amines in the presence of triethylamine to obtain compound 4.

[0088] As the acid binding agent used in the above substitution reaction, one or more of the acid binding agents known in the art, such as pyridine, triethylamine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like, is preferably used, with triethylamine being most preferred.

[0089] As the amount of base used in the above substitution reaction, 1 to 3 equivalents (molar ratio) relative to the amount of compound 3 is preferably used, with 1.5 equivalents (molar ratio) being most preferred.

[0090] As the solvent used in the above substitution reaction, one or more of dichloromethane, diethyl ether, carbon tetrachloride, toluene, benzene, and the like is preferably used, with dichloromethane being most preferred.

[0091] As the amount of different substituted alcohols or amines used in the above substitution reaction, 1 to 3 equivalents (molar ratio) relative to the amount of compound 3 is preferably used, with 1.1 equivalents (molar ratio) being most preferred.

[0092] As the temperature of the above substitution reaction, 25 to 40°C is preferred.

[0093] As the time of the above substitution reaction, 2 to 6 hours is preferred.

[0094] 4) Synthesis of compound 5 from compound 1 (substitution reaction)

[0095] The synthesis of compound 5 from compound 1 is preferably carried out by substitution reaction of compound 1 with 3-hydroxydihydrofuran-2(3H)-one in the presence of trimethylaluminum to obtain compound 5.

[0096] As the amount of 3-hydroxydihydrofuran-2(3H)-one used in the above substitution reaction, 1 to 3 equivalents (molar ratio) relative to the amount of compound 1 is preferably used, with 1.2 equivalents (molar ratio) being most preferred.

[0097] As the amount of trimethylaluminum used in the above substitution reaction, 1 to 3 equivalents (molar ratio) relative to the amount of compound 1 is preferably used, with 1.3 equivalents (molar ratio) being most preferred.

[0098] As the temperature of the above substitution reaction, 0 to 30°C is preferred.

[0099] As the time of the above substitution reaction, 4 to 8 hours is preferred.

[0100] 5) Synthesis of compound 6 from compound 5 (substitution reaction)

[0101] The synthesis of compound 6 from compound 5 is preferably a substitution reaction of compound 5 with triphenylphosphine and carbon tetrabromide to form a bromide intermediate, followed by reaction with 1,8-diazabicyclo[5,4,0]undec-7-ene to form compound 6.

[0102] As the amount of triphenylphosphine used in the above, 1 to 3 equivalents (molar ratio) relative to the amount of compound 5 are preferably used, and 1.5 equivalents (molar ratio) are more preferably used.

[0103] As the amount of carbon tetrabromide used in the above, 1 to 3 equivalents (molar ratio) relative to the amount of compound 5 are preferably used, and 1.5 equivalents (molar ratio) are more preferably used.

[0104] As the base used in the above substitution reaction, one or more of 1,8-diazabicyclo[5,4,0]undec-7-ene, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, cesium carbonate, sodium tert-butoxide, sodium ethoxide, and sodium hydride are preferably used, and 1,8-diazabicyclo[5,4,0]undec-7-ene is more preferably used.

[0105] As the amount of 1,8-diazabicyclo[5,4,0]undec-7-ene used in the above reaction, 1 to 3 equivalents (molar ratio) relative to the amount of the intermediate bromide are preferably used, and 2 equivalents (molar ratio) are more preferably used.

[0106] As the temperature of the above substitution reaction, 0 to 30°C is preferable.

[0107] As the time of the above substitution reaction, 4 to 8 hours is preferable.

[0108] 6) Synthesis of compound 7 from compound 6 (substitution reaction)

[0109] The synthesis of compound 7 from compound 6 is preferably a substitution reaction of compound 6 with a different substituted acyl chloride in the presence of triethylamine to form compound 7.

[0110] As the acid binding agent used in the above substitution reaction, the acid binding agent is well known in the art, such as one or more of pyridine, triethylamine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, and the like, and triethylamine is preferably used.

[0111] As the amount of base used in the above substitution reaction, 1 to 3 equivalents (molar ratio) relative to the amount of compound 6 are preferably used, and 1.5 equivalents (molar ratio) are more preferably used.

[0112] As the solvent used in the above substitution reaction, preferably one or more of dichloromethane, diethyl ether, carbon tetrachloride, toluene, benzene, etc., preferably dichloromethane as the solvent.

[0113] As the amount of acyl chloride used in the above substitution reaction, preferably 1-3 equivalents (molar ratio) relative to the amount of compound 6, more preferably 1.1 equivalents (molar ratio) is used.

[0114] As the temperature of the above substitution reaction, preferably 25-40℃.

[0115] As the time of the above substitution reaction, preferably 2-6 hours.

[0116] The present application also provides the use of the above technical solution pyrrolidone-containing 2-phenylpyridine derivatives in the prevention and control of weeds. In the present application, the weeds preferably include one or more of amaranthus retroflexus, abutilon theophrasti, medicago polymorpha, euphorbia heterophylla, digitaria sanguinalis, lolium multiflorum, setaria viridis and malvastrum coromandelianum. In the present application, the use amount of the pyrrolidone-containing 2-phenylpyridine derivative is preferably 9.375-150 g ai / ha, more preferably 37.5-75 g ai / ha.

[0117] The present application also provides a herbicide comprising the pyrrolidone-containing 2-phenylpyridine derivative described in the above technical solution. The present application does not have special limitations on the dosage form of the herbicide, and any dosage form acceptable to the pyrrolidone-containing 2-phenylpyridine derivative can be used. The present application does not have special limitations on the preparation method of the herbicide, and any conventional preparation method can be used.

[0118] In order to further illustrate the present application, the present application will be described in detail below in conjunction with examples, but they should not be understood as limiting the scope of protection of the present application.

[0119] The chemical reagents used in the following examples, unless otherwise specified, are commercially available.

[0120] In the following examples, the determination of nuclear magnetic resonance data was carried out by using Bruker ASCEND 400 (400 MHz) nuclear magnetic resonance instrument, and the determination of mass spectrometry data was carried out by using Thermo Fisher Q Exactive mass spectrometer.

[0121] Example 1

[0122] This example is used to illustrate the preparation method of the pyrrolidone-containing 2-phenylpyridine derivative of the present application, and the examples of representative compounds include the following steps:

[0123] (1) Synthesis of compound 2:

[0124]

[0125] Compound 1 (3.0 g, 9.23 mmol) was added to a round bottom flask containing 20 mL of acetonitrile (CH3CN) and stirred under nitrogen. The reaction was continued at 60 °C for 3 hours, cooled to room temperature and concentrated. The mixture was purified by column chromatography using dichloromethane / methanol (30:1) as eluent to obtain the product 2.

[0126] (2) Synthesis of compound 3:

[0127]

[0128] Compound 2 (1.0 g, 2.29 mmol) was dissolved in dry dichloromethane (DCM) and oxalyl chloride (290.32 μL, 3.43 mmol) was added. After 30 minutes of reaction at room temperature, 2 drops of N,N-dimethylformamide (DMF) were added and the reaction was continued for 2 hours at room temperature, then compound 3 was obtained by vacuum concentration.

[0129] (3) Synthesis of compound 4:

[0130]

[0131] Triethylamine (Et3N, 0.15 g 1.5 mmol) was added to a solution of amine or alcohol (1.1 mmol) in DCM (3 mL) at 0 °C. After stirring for 10 minutes at 0 °C, compound 3 (1.0 mmol) was added and stirred at room temperature for 3 hours. After completion of the reaction, the mixture was separated by column chromatography using petroleum ether / ethyl acetate (5:1 to 1:1) as eluent to obtain the product 4.

[0132] (4) Synthesis of compound 5:

[0133]

[0134] Compound 1 (1.0 g, 3.08 mmol) was dissolved in dry DCM (10 mL) under nitrogen at 0 °C and a solution of trimethylaluminum in hexane (2.0 M, 4 mmol) was slowly added, stirring for 30 minutes at room temperature and then cooling to 0 °C. A solution of 3-hydroxydihydrofuran-2(3H)-one (287.89 μL, 3.69 mmol) in DCM (2.0 mL) was slowly added dropwise to the reaction. After 4 hours, the reaction was brought to 0 °C, 1.0 M aqueous HCl was added and the organic phase was washed twice, then purified by column chromatography to obtain compound 5.

[0135] (5) Synthesis of compound 6:

[0136]

[0137] Compound 5 (1.86 g, 4.35 mmol) was dissolved in dry DCM (15 mL), cooled to 0 °C, and a solution of triphenylphosphine (PPh3, 1.71 g, 6.53 mmol) in DCM (3.0 mL) was slowly added to the reaction solution, while slowly adding a solution of carbon tetrabromide (CBr4, 2.17 g, 6.53 mmol) in DCM (4.0 mL). The reaction was allowed to proceed for 10 minutes at 0 °C, and then stirred for 4 hours at room temperature. After the reaction was completed, the reaction solution was diluted with dry DCM, and the organic layer was washed with saturated aqueous NaHCO3solution and brine, and the bromide was concentrated. The bromide compound (1 mmol) was dissolved in chloroform under nitrogen, and 1,8-diazabicyclo[5,4,0]undec-7-ene (DBU, 2 mmol) was added and reacted for 1 hour at room temperature. The reaction solution was diluted with DCM, and the organic layer was washed with 1 M aqueous HC1, saturated aqueous NaHCO3solution, and brine, and the mixture was isolated and purified by column chromatography to obtain compound 6.

[0138] (6) Synthesis of compound 7:

[0139]

[0140] Triethylamine (0.15 g, 1.5 mmol) was added to compound 6 (0.408 g, 1.0 mmol) in 3 mL of DCM at 0 °C. After stirring for 30 minutes at 0 °C, the acyl chloride (1.0 mmol) was added and stirred for 3 hours at room temperature. After the reaction was completed, the mixture was isolated and purified by column chromatography using petroleum ether / ethyl acetate (5:1 ~ 1:1) as an eluent to obtain product 7.

[0141] The structural formula and molecular formula of the target compounds synthesized in the above examples are shown in Table 1.

[0142] The structural formula and molecular formula of the target compounds 4 and 7 prepared in Example 1 of the present application are shown in Table 1, and compounds 4a ~ 4w can be obtained by the synthesis steps of steps (1) ~ (3); and compounds 7a ~ 7g can be obtained by the synthesis steps of steps (4) ~ (6).

[0143] Table 1 Chemical structure of 2-phenylpyridine derivatives containing pyrrolidone

[0144]

[0145]

[0146] 4a: yellow solid, yield: 75%, melting point: 41-43 °C. 1 H NMR (400 MHz, CDC13) δ 8.87-8.81 (m, 1H), 8.09-8.03 (m, 1H), 7.45 (d, J = 6.8 Hz, 1H), 7.40-7.30 (m, 2H), 3.83-3.73 (m, 2H), 3.43 (dd, J = 9.6, 8.4 Hz, 1H), 3.39-3.23 (m, 2H), 2.78-2.64 (m, 1H), 2.57-2.44 (m, 1H), 1.14 (t, J = 7.3 Hz, 3H). 13 C NMR (101 MHz, CDC13) δ 172.7, 166.8, 158.6 (d, J = 256.1 Hz), 154.4, 144.4 (q, J = 3.9 Hz), 134.9 (q, J = 3.6 Hz), 134.8 (d, J = 10.8 Hz), 132.3, 132.2 (d, J = 3.7 Hz), 131.6 (d, J = 4.4 Hz), 127.5 (q, J = 33.8 Hz), 125.3 (d, J = 16.4 Hz), 122.5 (q, J = 273.3 Hz), 118.4 (d, J = 26.2 Hz), 48.3, 46.7, 34.6, 21.7, 14.6. HRMS (ESI): calcd for C 19 H 15 Cl2F4N3O2[M+Na] + 486.0370, found: 486.0376.

[0147] 4b: pale yellow solid, yield: 70%, mp: 43-45 °C. 1 H NMR (400 MHz, CDC13) δ 8.86-8.80 (m, 1H), 8.05 (dd, J = 2.1, 0.7 Hz, 1H), 7.44 (d, J = 6.8 Hz, 1H), 7.41-7.33 (m, 2H), 3.82-3.71 (m, 2H), 3.44 (dd, J = 9.6, 8.4 Hz, 1H), 3.29-3.18 (m, 2H), 2.78-2.65 (m, 1H), 2.56-2.43 (m, 1H), 1.59-1.47 (m, 2H), 0.91 (t, J = 7.4 Hz, 3H). 13 C NMR(101 MHz, CDCI3) δ 172.7, 166.9, 158.6 (d, J = 256.1 Hz), 154.4, 144.4 (q, J = 3.8 Hz), 134.9 (q, J = 3.5 Hz), 134.9 (d, J = 11.0 Hz), 132.3 (d, J = 3.2 Hz), 132.3, 131.6 (d, J = 4.4 Hz), 127.5 (q, J = 33.9 Hz), 125.3 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.3 Hz), 48.3, 46.8, 41.4, 22.7, 21.7, 11.4. HRMS (ESI): calcd for C 20 H 17 Cl2F4N3O2[M+Na] + 500.0526, found: 500.0536.

[0148] 4c: white solid, yield: 75%, m.p.: 53-55 °C. 1 H NMR (400 MHz, CDCI3) δ 8.86-8.81 (m, 1H), 8.06 (dd, J = 2.0, 0.8 Hz, 1H), 7.46 (d, J = 6.8 Hz, 1H), 7.37 (d, J = 9.0 Hz, 1H), 7.19 (d, J = 7.8 Hz, 1H), 4.15-4.03 (m, 1H), 3.84-3.71 (m, 2H), 3.40 (dd, J = 9.6, 8.3 Hz, 1H), 2.79-2.65 (m, 1H), 2.55-2.43 (m, 1H), 1.16 (dd, J = 11.7, 6.5 Hz, 6H). 13 C NMR (101 MHz, CDCI3) δ 172.7, 165.9, 158.6 (d, J = 256.1 Hz), 154.4, 144.4 (q, J = 3.9 Hz), 134.9 (q, J = 3.6 Hz), 134.8 (d, J = 10.7 Hz), 132.2 (d, J = 2.9 Hz), 132.2, 131.5 (d, J = 4.4 Hz), 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.5 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 48.3, 46.8, 41.7, 22.6, 21.6. HRMS (ESI): calcd for C 20 H 17 Cl2F4N3O2[M+Na] +500.0526, found: 500.0526.

[0149] 4d: yellow viscous liquid, yield: 72%. 1 H NMR (400 MHz, CDCI3) δ 8.82 (dt, J = 1.9, 0.9 Hz, 1 H), 8.05 (d, J = 1.9 Hz, 1 H), 7.44 (d, J = 6.8 Hz, 1 H), 7.39 - 7.32 (m, 2 H), 3.82 - 3.72 (m, 2 H), 3.43 (dd, J = 9.6, 8.3 Hz, 1 H), 3.36 - 3.18 (m, 2 H), 2.77 - 2.63 (m, 1 H), 2.55 - 2.42 (m, 1 H), 1.54 - 1.42 (m, 2 H), 1.39 - 1.26 (m, 2 H), 0.88 (t, J = 7.3 Hz, 3 H). 13 C NMR (101 MHz, CDCI3) δ 172.8, 166.9, 158.6 (d, J = 256.1 Hz), 154.4 (d, J = 2.0 Hz), 144.4 (q, J = 3.9 Hz), 134.9 (q, J = 3.7 Hz), 134.9 (d, J = 10.7 Hz), 132.3 (d, J = 3.9 Hz), 132.3, 131.6 (d, J = 4.4 Hz), 127.4 (q, J = 33.8 Hz), 125.3 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 48.4, 46.8, 39.4, 31.5, 21.7, 20.1, 13.7. HRMS (ESI): calcd for C 21 H 19 Cl2F4N3O2[M+Na] + 514.0683, found: 514.0689.

[0150] 4e: white solid, yield: 73%, m.p. 120-122 °C. 1 H NMR (400 MHz, CDCI3) δ 8.87 - 8.81 (m, 1 H), 8.09 - 8.03 (m, 1 H), 7.46 (d, J = 6.8 Hz, 1 H), 7.36 (d, J = 9.0 Hz, 1 H), 7.21 (s, 1 H), 3.83 - 3.68 (m, 2 H), 3.38 (dd, J = 9.7, 8.3 Hz, 1 H), 2.77 - 2.63 (m, 1 H), 2.51 - 2.38 (m, 1 H), 1.35 (s, 9 H). 13 C NMR(101 MHz, CDCI3) δ 172.9, 165.8, 158.6 (d, J = 256.2 Hz), 154.4, 144.4 (q, J = 3.9 Hz), 134.9 (q, J = 3.7 Hz), 134.9 (d, J = 11.2 Hz), 132.3 (d, J = 4.4 Hz), 132.3, 131.6 (d, J = 4.4 Hz), 127.4 (q, J = 33.8 Hz), 125.3 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.3 Hz), 51.3, 48.3, 47.3, 28.7, 21.4. HRMS (ESI): calcd for C 21 H 19 Cl2F4N3O2[M+Na]+514.0683, found: 514.0683.

[0151] 4f: white solid, yield: 76%, melting point: 78-80 °C. 1 H NMR (400 MHz, CDCI3) δ 8.82 (dd, J = 2.0, 0.9 Hz, 1 H), 8.04 (d, J = 2.0 Hz, 1 H), 7.72 (t, J = 5.8 Hz, 1 H), 7.43 (d, J = 6.8 Hz, 1 H), 7.34 (d, J = 9.1 Hz, 1 H), 7.30-7.24 (m, 4 H), 7.23-7.18 (m, 1 H), 4.55-4.38 (m, 2 H), 3.82-3.70 (m, 2 H), 3.48 (dd, J = 9.6, 8.2 Hz, 1 H), 2.80-2.66 (m, 1 H), 2.55-2.42 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 172.5, 167.0, 158.6 (d, J = 256.1 Hz), 154.4, 144.4 (q, J = 3.9 Hz), 138.0, 134.9 (q, J = 3.5 Hz), 134.8 (d, J = 11.0 Hz), 132.2 (d, J = 3.9 Hz), 132.2, 131.5 (d, J = 4.4 Hz), 128.6, 127.6, 127.4 (q, J = 33.9 Hz), 127.4, 125.3 (d, J = 16.3 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.3 Hz), 48.4, 46.9, 43.7, 21.6. HRMS (ESI): calcd for C 24 H 17 Cl2F4N3O2[M+Na] +548.0526, found: 548.0523.

[0152] 4g: white solid, yield: 68%, m.p.: 121-123 °C. 1 H NMR (400 MHz, CDC13) δ 8.84 (dd, J = 1.9, 0.9 Hz, 1H), 8.07 (d, J = 2.0 Hz, 1H), 7.68 (t, J = 5.8 Hz, 1H), 7.45 (d, J = 6.8 Hz, 1H), 7.36 (d, J = 9.1 Hz, 1H), 7.17 (dd, J = 8.1 Hz, 2H), 7.10 (dd, J = 8.0 Hz, 2H), 4.54 - 4.35 (m, 2H), 3.86 - 3.72 (m, 2H), 3.48 (dd, J = 9.6, 8.3 Hz, 1H), 2.83 - 2.68 (m, 1H), 2.57 - 2.45 (m, 1H), 2.30 (s, 3H). 13 C NMR (101 MHz, CDC13) δ 172.5, 166.9, 158.6 (d, J = 256.0 Hz), 154.4, 144.4 (q, J = 3.9 Hz), 137.0, 135.0, 134.9 (q, J = 3.2 Hz), 134.8 (d, J = 10.2 Hz), 132.2, 132.2 (d, J = 3.3 Hz), 131.5 (d, J = 4.4 Hz), 129.3, 127.7, 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 48.3, 46.9, 43.5, 21.6, 21.1. HRMS (ESI): calcd for C 25 H 19 Cl2F4N3O2[M+Na] + 562.0683, found: 562.0684.

[0153] 4h: pale yellow solid, yield: 72%, m.p.: 55-57 °C. 1 H NMR(400 MHz, CDCI3) δ 8.85 (dd, J = 2.0, 1.0 Hz, 1 H), 8.07 (d, J = 2.0 Hz, 1 H), 7.74 (t, J = 5.9 Hz, 1 H), 7.45 (d, J = 6.9 Hz, 1 H), 7.37 (d, J = 9.1 Hz, 1 H), 7.27-7.20 (m, 2 H), 7.02-6.94 (m, 2 H), 4.51-4.38 (m, 2 H), 3.85-3.75 (m, 2 H), 3.50 (dd, J = 9.6, 8.3 Hz, 1 H), 2.82-2.70 (m, 1 H), 2.59-2.46 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 172.4, 167.0, 162.1 (d, J = 245.4 Hz), 158.6 (d, J = 256.2 Hz), 154.3, 144.4 (q, J = 3.9 Hz), 134.9 (q, J = 3.6 Hz), 134.8 (d, J = 10.9 Hz), 133.9 (d, J = 3.1 Hz), 132.2, 132.1 (d, J = 3.7 Hz), 131.5 (d, J = 4.4 Hz), 129.3 (d, J = 8.1 Hz), 127.5 (q, J = 33.9 Hz), 125.3 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 115.4 (d, J = 21.4 Hz), 48.4, 46.9, 42.9, 21.5. 19 F NMR (376 MHz, Chloroform-d) δ -62.3, -109.2, -115.3. HRMS (ESI): calcd for C 24 H 16 Cl2F5N3O2[M+Na] + 566.0432, found: 566.0437.

[0154] 4i: White solid, yield: 74%, m.p. 58-60 °C. 1 H NMR (400 MHz, CDCI3) δ 8.85 (dd, J = 2.0, 1.0 Hz, 1 H), 8.07 (d, J = 2.0 Hz, 1 H), 7.74 (t, J = 6.0 Hz, 1 H), 7.45 (d, J = 6.8 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H), 7.30-7.18 (m, 4 H), 4.44 (d, J = 5.9 Hz, 2 H), 3.85-3.75 (m, 2 H), 3.50 (dd, J = 9.6, 8.3 Hz, 1 H), 2.82-2.68 (m, 1 H), 2.58-2.45 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 172.4, 167.1, 158.6 (d, J = 256.3 Hz), 154.3, 144.4 (q, J = 4.0 Hz), 136.6, 134.9 (q, J = 3.6 Hz), 134.8 (d, J = 10.7 Hz), 133.1, 132.2, 132.1 (d, J = 3.7 Hz), 131.5 (d, J = 4.4 Hz), 129.0, 128.8, 127.5 (q, J = 33.9 Hz), 125.3 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 48.4, 46.9, 42.9, 21.5. HRMS (ESI): calcd for C 24 H 16 Cl3F4N3O2[M+Na] + 582.0136, found: 582.0103.

[0155] 4j: pale yellow solid, yield: 70%, m.p. 60-62 °C. 1 H NMR (400 MHz, CDCI3) δ 8.85 (dd, J = 2.0, 0.9 Hz, 1 H), 8.08 (d, J = 1.9 Hz, 1 H), 7.67 (t, J = 5.3 Hz, 1 H), 7.47 (d, J = 6.8 Hz, 1 H), 7.38 (d, J = 9.0 Hz, 1 H), 4.19-3.99 (m, 2H), 3.85-3.73 (m, 2H), 3.49 (t, J = 9.1 Hz, 1 H), 2.80-2.65 (m, 1 H), 2.60-2.47 (m, 1 H), 2.21 (t, J = 2.5 Hz, 1 H). 13 C NMR (101 MHz, CDCI3) δ 172.2, 166.9, 158.6 (d, J = 256.2 Hz), 154.3, 144.4 (t, J = 4.0 Hz), 134.9 (q, J = 3.5 Hz), 134.8 (d, J = 10.8 Hz), 132.2, 132.1 (d, J = 3.7 Hz), 131.5 (d, J = 4.4 Hz), 127.5 (q, J = 34.0 Hz), 125.3 (d, J = 16.5 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 79.2, 71.6, 48.2, 46.7, 29.3, 21.5. HRMS (ESI): calcd for C 20 H 13 C l2F4N2O2[M+Na]+ 496.0213, found: 496.0225.

[0156] 4k: white solid, yield: 85%, melting point: 92-94 °C. 1 H NMR (400 MHz, CDCI3) δ 8.85-8.80 (m, 1 H), 8.05 (dd, J = 2.0, 0.8 Hz, 1 H), 7.47 (d, J = 6.9 Hz, 1 H), 7.34 (d, J = 9.1 Hz, 1 H), 3.93-3.76 (m, 5H), 3.62 (dd, J = 9.2, 6.5 Hz, 1 H), 2.67-2.54 (m, 1 H), 2.54-2.40 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 170.0, 169.7, 158.5 (d, J = 255.7 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 134.9 (q, J = 3.4 Hz), 134.8 (d, J = 10.3 Hz), 132.3 (d, J = 3.7 Hz), 132.2, 131.7 (d, J = 4.3 Hz), 127.4 (q, J = 33.9 Hz), 125.1 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.2 Hz), 52.8, 48.4, 48.1, 23.3. HRMS (ESI): calcd for C 18 H 12 Cl2F4N2O3[M+Na]+ 473.0053, found: 473.0054.

[0157] 4l: white solid, yield: 88%, melting point: 88-90 °C. 1 H NMR (400 MHz, CDCI3) δ 8.85-8.80 (m, 1 H), 8.05 (dd, J = 2.0, 0.7 Hz, 1 H), 7.48 (d, J = 6.9 Hz, 1 H), 7.34 (d, J = 9.0 Hz, 1 H), 4.32-4.16 (m, 2H), 3.94-3.84 (m, 1 H), 3.84-3.75 (m, 1 H), 3.59 (dd, J = 9.2, 6.4 Hz, 1 H), 2.66-2.53 (m, 1 H), 2.53-2.40 (m, 1 H), 1.29 (t, J = 7.2 Hz, 3H). 13 C NMR(101 MHz, CDCI3) δ 169.9, 169.6, 158.5 (d, J = 255.5 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 134.9 (q, J = 3.6 Hz), 134.8 (d, J = 10.6 Hz), 132.4 (d, J = 3.7 Hz), 132.2, 131.8 (d, J = 4.4 Hz), 127.3 (q, J = 33.9 Hz), 125.1 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.1 Hz), 61.8, 48.5, 48.2, 23.4, 14.1. HRMS (ESI): calcd for C 19 H 14 Cl2F4N2O3[M+Na]+487.0210, found: 487.0209.

[0158] 4m: colorless viscous liquid, yield: 85%. 1 H NMR (400 MHz, CDCI3) δ 8.85-8.79 (m, 1H), 8.05 (dd, J = 2.0, 0.8 Hz, 1H), 7.48 (d, J = 6.9 Hz, 1H), 7.34 (d, J = 9.1 Hz, 1H), 4.23-4.07 (m, 2H), 3.94-3.84 (m, 1H), 3.84-3.75 (m, 1H), 3.60 (dd, J = 9.2, 6.4 Hz, 1H), 2.67-2.54 (m, 1H), 2.54-2.40 (m, 1H), 1.74-1.63 (m, 2H), 0.95 (t, J = 7.5 Hz, 3H). 13 C NMR (101 MHz, CDCI3) δ 169.9, 169.7, 158.5 (d, J = 255.8 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 134.9 (d, J = 10.7 Hz), 134.9 (q, J = 3.6 Hz), 132.4 (d, J = 3.7 Hz), 132.2, 131.8 (d, J = 4.4 Hz), 127.3 (q, J = 33.8 Hz), 125.1 (d, J = 16.4 Hz), 122.5 (q, J = 273.1 Hz), 118.3 (d, J = 26.1 Hz), 67.4, 48.5, 48.3, 23.4, 21.9, 10.3. HRMS (ESI): calcd for C 20 H 16 Cl2F4N2O3[M+Na]+501.0366, found: 501.0365.

[0159] 4n: white solid, yield: 86%, m.p.: 119-121 °C. 1 H NMR (400 MHz, CDC13) δ 8.87-8.81 (m, 1H), 8.06 (dd, J = 2.0, 0.8 Hz, 1H), 7.49 (d, J = 6.9 Hz, 1H), 7.35 (d, J = 9.0 Hz, 1H), 5.17-5.03 (m, 1H), 3.96-3.85 (m, 1H), 3.85-3.74 (m, 1H), 3.56 (dd, J = 9.2, 6.4 Hz, 1H), 2.66-2.54 (m, 1H), 2.54-2.40 (m, 1H), 1.29 (dd, J = 6.3, 2.3 Hz, 6H). 13 C NMR (101 MHz, CDC13) δ 170.0, 169.2, 158.5 (d, J = 255.5 Hz), 154.5, 144.3 (q, J = 4.0 Hz), 134.9 (d, J = 10.8 Hz), 134.9 (q, J = 3.6 Hz), 132.4 (d, J = 3.7 Hz), 132.3, 131.8 (d, J = 4.4 Hz), 127.4 (q, J = 33.9 Hz), 125.1 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.1 Hz), 69.5, 48.4, 23.4, 21.7 (d, J = 4.2 Hz). HRMS (ESI): calcd for C 20 H 16 Cl2F4N2O3[M+Na] + 501.0366, found: 501.0360.

[0160] 4o: colorless viscous liquid, yield: 81%. 1 H NMR (400 MHz, CDC13) δ 8.84 (dd, J = 2.0, 1.0 Hz, 1H), 8.07 (d, J = 1.9 Hz, 1H), 7.49 (d, J = 6.9 Hz, 1H), 7.36 (d, J = 9.0 Hz, 1H), 4.29-4.13 (m, 2H), 3.96-3.76 (m, 2H), 3.61 (dd, J = 9.2, 6.4 Hz, 1H), 2.67-2.42 (m, 2H), 1.73-1.61 (m, 2H), 1.48-1.34 (m, 2H), 0.92 (t, J = 7.4 Hz, 3H). 13 C NMR(101 MHz, CDCI3) δ 169.9, 169.7, 158.5 (d, J = 255.7 Hz), 154.5, 144.3 (q, J = 3.8 Hz), 134.9 (d, J = 10.8 Hz), 134.9 (q, J = 3.6 Hz), 132.4 (d, J = 3.7 Hz), 132.2, 131.8 (d, J = 4.3 Hz), 127.4 (q, J = 33.9 Hz), 125.1 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.1 Hz), 65.7, 48.5, 48.3, 30.6, 23.4, 19.0, 13.6. HRMS (ESI): calcd for C 21 H 18 Cl2F4N2O3[M+Na]+515.0523, found: 515.0513.

[0161] 4p: white solid, yield: 79%, melting point: 134-136 °C. 1 H NMR (400 MHz, CDCI3) δ 8.84 (d, J = 1.4 Hz, 1H), 8.06 (d, J = 2.0 Hz, 1H), 7.49 (d, J = 6.9 Hz, 1H), 7.35 (d, J = 9.1 Hz, 1H), 3.95-3.84 (m, 1H), 3.83-3.73 (m, 1H), 3.50 (dd, J = 9.2, 6.2 Hz, 1H), 2.63-2.51 (m, 1H), 2.51-2.38 (m, 1H), 1.51 (s, 9H). 13 C NMR (101 MHz, CDCI3) δ 170.3, 168.8, 158.4 (d, J = 255.5 Hz), 154.6, 144.3 (q, J = 4.0 Hz), 134.9 (d, J = 10.7 Hz), 134.9 (q, J = 3.7 Hz), 132.5 (d, J = 3.7 Hz), 132.3, 131.8 (d, J = 4.4 Hz), 127.3 (q, J = 33.8 Hz), 125.1 (d, J = 16.3 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.2 Hz), 82.3, 49.3, 48.4, 28.0, 23.4. HRMS (ESI): calcd for C 21 H 18 Cl2F4N2O3[M+Na]+515.0523, found: 515.0513.

[0162] 4q: pale yellow viscous liquid, yield: 84%. 1 H NMR (400 MHz, CDC13) δ 8.87 - 8.81 (m, 1H), 8.08 - 8.03 (m, 1H), 7.51 (d, J = 6.9 Hz, 1H), 7.37 (s, 1H), 4.80 - 4.63 (m, 2H), 4.22 (q, J = 7.2 Hz, 2H), 3.98 - 3.81 (m, 2H), 3.73 (dd, J = 9.3, 6.0 Hz, 1H), 2.75 - 2.63 (m, 1H), 2.63 - 2.49 (m, 1H), 1.28 (t, J = 7.2 Hz, 3H). 13 C NMR (101 MHz, CDC13) δ 169.4, 169.1, 167.3, 158.5 (d, J = 255.8 Hz), 154.5, 144.3 (q, J = 3.8 Hz), 134.9 (d, J = 10.7 Hz), 134.9 (q, J = 3.7 Hz), 132.3, 132.3 (d, J = 2.5 Hz), 131.8 (d, J = 4.3 Hz), 127.4 (q, J = 33.8 Hz), 125.2 (d, J = 16.3 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.2 Hz), 61.6, 61.5, 48.5, 48.0, 23.6, 14.1. HRMS (ESI): calcd for C 21 H 16 Cl2F4N2O5[M+Na]+545.0265, found: 545.0265.

[0163] 4r: white solid, yield: 84%, melting point: 122-124 °C. 1 H NMR (400 MHz, CDC13) δ 8.83 (d, J = 2.0 Hz, 1H), 8.05 (d, J = 2.0 Hz, 1H), 7.44 (d, J = 6.8 Hz, 1H), 7.41 - 7.23 (m, 6H), 5.23 (s, 2H), 3.91 - 3.74 (m, 2H), 3.66 (dd, J = 9.2, 6.3 Hz, 1H), 2.67 - 2.54 (m, 1H), 2.54 - 2.40 (m, 1H). 13 C NMR(101 MHz, CDCI3) δ 169.7, 169.4, 158.5 (d, J = 255.6 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 135.4, 134.9 (d, J = 11.4 Hz), 134.9 (q, J = 3.8 Hz), 132.4 (d, J = 3.6 Hz), 132.2, 131.8 (d, J = 4.3 Hz), 128.6, 128.3, 128.2, 127.3 (q, J = 33.9 Hz), 125.2 (d, J = 16.3 Hz), 122.5 (q, J = 273.2 Hz), 1 18.3 (d, J = 26.2 Hz), 67.4, 48.5, 48.3, 23.4. HRMS (ESI): calcd for C 24 H 16 Cl2F4N2O3[M+Na]+549.0366, found: 549.0356.

[0164] 4s: white solid, yield: 82%, melting point: 108-110 °C. 1 H NMR (400 MHz, CDCI3) δ 8.87-8.81 (m, 1 H), 8.06 (d, J = 2.6 Hz, 1 H), 7.47 (d, J = 6.9 Hz, 1 H), 7.34 (d, J = 9.0 Hz, 1 H), 7.30-7.25 (m, 2 H), 7.18-7.1 1 (m, 2 H), 5.19 (s, 2 H), 3.92-3.74 (m, 2 H), 3.65 (dd, J = 9.2, 6.4 Hz, 1 H), 2.67-2.54 (m, 1 H), 2.54-2.41 (m, 1 H), 2.32 (s, 3 H). 13 C NMR (101 MHz, CDCI3) δ 169.6, 169.3, 158.3 (d, J = 255.7 Hz), 154.4, 144.1 (q, J = 4.0 Hz), 138.0, 134.8 (d, J = 11.8 Hz), 134.7 (d, J = 3.4 Hz), 132.2, 132.2 (d, J = 4.4 Hz), 132.1, 131.6 (d, J = 4.4 Hz), 129.1, 128.2, 127.2 (q, J = 33.8 Hz), 125.0 (d, J = 16.3 Hz), 122.3 (q, J = 273.2 Hz), 1 18.2 (d, J = 26.1 Hz), 67.3, 48.3, 48.1, 23.2, 21.0. HRMS (ESI): calcd for C 25 H 18Cl2F4N2O3[M+Na]+ 563.0523, found: 563.0521.

[0165] 4t: white solid, yield: 80%, m.p.: 110-112 °C. 1 H NMR (400 MHz, CDCI3) δ 8.84 (d, J = 1.9 Hz, 1 H), 8.07 (d, J = 2.0 Hz, 1 H), 7.60 (d, J = 8.1 Hz, 2 H), 7.52 (d, J = 8.1 Hz, 2 H), 7.48 (d, J = 6.8 Hz, 1 H), 7.36 (d, J = 9.0 Hz, 1 H), 5.34 (d, J = 13.0 Hz, 1 H), 5.26 (d, J = 13.0 Hz, 1 H), 3.94 - 3.77 (m, 2 H), 3.76 - 3.68 (m, 1 H), 2.72 - 2.59 (m, 1 H), 2.57 - 2.44 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 169.5, 169.2, 158.6 (d, J = 255.8 Hz), 154.4, 144.3 (q, J = 3.9 Hz), 139.5 (d, J = 1.6 Hz), 134.9 (q, J = 3.6 Hz), 134.9 (d, J = 10.8 Hz), 132.2 (d, J = 4.0 Hz), 132.2, 131.7 (d, J = 4.3 Hz), 130.3 (q, J = 32.5 Hz), 127.9, 127.4 (q, J = 33.8 Hz), 125.5 (q, J = 3.8 Hz), 125.2 (d, J = 16.4 Hz), 124.0 (q, J = 272.1 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 66.3, 48.4, 48.2, 23.2. 19 F NMR (376 MHz, CDCI3) δ -62.4, -62.7, -109.6. HRMS (ESI): calcd for C 25 H 15 Cl2F7N2O3[M+Na]+ 617.0240, found: 617.0234.

[0166] 4u: white solid, yield: 77%, m.p.: 123-125 °C. 1 H NMR(400 MHz, CDCI3) δ 8.83 (dd, J = 2.1, 0.9 Hz, 1 H), 8.06 (d, J = 2.0 Hz, 1 H), 7.42 (d, J = 6.9 Hz, 1 H), 7.40-7.31 (m, 3 H), 7.05-6.95 (m, 2 H), 5.19 (dd, J = 2.6 Hz, 2 H), 3.92-3.75 (m, 2 H), 3.65 (dd, J = 9.2, 6.4 Hz, 1 H), 2.68-2.55 (m, 1 H), 2.55-2.41 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 168.9, 168.6, 161.9 (d, J = 246.9 Hz), 157.8 (d, J = 255.9 Hz), 153.7, 143.6 (q, J = 3.9 Hz), 134.2 (d, J = 10.8 Hz), 134.2 (q, J = 3.6 Hz), 131.5 (d, J = 3.7 Hz), 131.5, 131.0 (d, J = 4.4 Hz), 130.5 (d, J = 3.3 Hz), 129.4 (d, J = 8.3 Hz), 126.6 (q, J = 33.9 Hz), 124.4 (d, J = 16.4 Hz), 121.8 (q, J = 273.2 Hz), 117.6 (d, J = 26.2 Hz), 114.8 (d, J = 21.6 Hz), 65.9, 47.7, 47.5, 22.5. 19 F NMR (376 MHz, CDCI3) δ -62.3, -109.7, -113.4. HRMS (ESI): calcd for C 24 H 15 Cl2F5N2O3[M+Na]+567.0272, found: 567.0273.

[0167] 4v: colorless viscous liquid, yield: 74%. 1 H NMR (400 MHz, CDCI3) δ 8.87-8.82 (m, 1 H), 8.07 (dd, J = 1.9, 0.8 Hz, 1 H), 7.50 (d, J = 6.9 Hz, 1 H), 7.37 (d, J = 9.1 Hz, 1 H), 4.76-4.64 (m, 1 H), 4.64-4.33 (m, 3 H), 3.96-3.79 (m, 2 H), 3.69 (dd, J = 9.2, 6.7 Hz, 1 H), 2.70-2.59 (m, 1 H), 2.59-2.46 (m, 1 H). 13 C NMR(101 MHz, CDCI3) δ 169.5, 169.5, 158.5 (d, J = 255.8 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 134.9 (q, J = 3.6 Hz), 134.9 (d, J = 10.8 Hz), 132.3 (d, J = 4.0 Hz), 132.3, 131.7 (d, J = 4.4 Hz), 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.2 Hz), 81.0 (d, J = 171.0 Hz), 64.4 (d, J = 20.4 Hz), 48.4, 48.1, 23.4. 19 F NMR (376 MHz, CDCI3) δ -62.3, -109.8. HRMS (ESI): calcd for C 19 H 13 Cl2F5N2O3 [M + Na]+ 505.0116, found: 505.0113.

[0168] 4w: colorless viscous liquid, yield: 71%. 1 H NMR (400 MHz, CDCI3) δ 8.85 (dd, J = 2.0, 0.9 Hz, 1 H), 8.07 (dd, J = 2.0, 0.8 Hz, 1 H), 7.49 (d, J = 6.9 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H), 6.17-5.80 (m, 1 H), 4.49-4.32 (m, 2 H), 3.96-3.79 (m, 2 H), 3.71 (dd, J = 9.2, 6.9 Hz, 1 H), 2.71-2.47 (m, 2 H). 13 C NMR (101 MHz, CDCI3) δ 169.5, 169.5, 158.5 (d, J = 255.8 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 134.9 (q, J = 3.6 Hz), 134.9 (d, J = 10.8 Hz), 132.3 (d, J = 4.0 Hz), 132.3, 131.7 (d, J = 4.4 Hz), 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.3 (d, J = 26.2 Hz), 81.0 (d, J = 171.0 Hz), 64.4 (d, J = 20.4 Hz), 48.4, 48.1, 23.4. 19 F NMR (376 MHz, CDCI3) δ -62.4, -109.5, -125.5, -125.7. HRMS(ESI): calcd for C 19 H 12 Cl2F6N2O3[M+Na]+523.0021, found: 523.0024.

[0169] 7a: white solid, yield: 78%, melting point: 145-147 °C. 1 H NMR (400 MHz, CDCI3) δ 8.85 (dd, J = 2.0, 0.9 Hz, 1 H), 8.07 (dd, J = 1.9, 0.8 Hz, 1 H), 7.51 (d, J = 6.8 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H), 5.47 (t, J = 8.3 Hz, 1 H), 3.90-3.68 (m, 2 H), 2.81 -2.68 (m, 1 H), 2.28-2.19 (m, 1 H), 2.18 (s, 3 H). 13 C NMR (101 MHz, CDCI3) δ 170.3, 170.1, 158.6 (d, J = 256.0 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 134.9 (q, J = 3.5 Hz), 134.6 (d, J = 10.7 Hz), 132.3, 132.3 (d, J = 3.6 Hz), 131.6 (d, J = 4.5 Hz), 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.4 Hz), 122.5 (q, J = 273.1 Hz), 1 18.4 (d, J = 26.3 Hz), 70.5, 46.4, 26.8, 20.8. HRMS (ESI): calcd for C 18 H 12 Cl2F4N2O3[M+Na]+473.0053, found: 473.0063.

[0170] 7b: colorless viscous liquid, yield: 81 %. 1 H NMR (400 MHz, CDCI3) δ 8.87-8.82 (m, 1 H), 8.07 (dd, J = 1.9, 0.8 Hz, 1 H), 7.51 (d, J = 6.9 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H), 5.49 (t, J = 8.3 Hz, 1 H), 3.90-3.73 (m, 2 H), 2.80-2.68 (m, 1 H), 2.57-2.36 (m, 2 H), 2.29-2.14 (m, 1 H), 1.19 (t, J = 7.5 Hz, 3 H). 13 C NMR(101 MHz, CDCI3) δ 173.8, 170.2, 158.6 (d, J = 255.9 Hz), 154.5, 144.3 (q, J = 4.0 Hz), 134.9 (q, J = 3.6 Hz), 134.6 (d, J = 10.7 Hz), 132.3 (d, J = 3.7 Hz), 132.3, 131.6 (d, J = 4.3 Hz), 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.6 Hz), 122.5 (q, J = 273.3 Hz), 118.4 (d, J = 26.1 Hz), 70.4, 46.4, 27.4, 26.8, 8.9. HRMS (ESI): calcd for C 19 H 14 Cl2F4N2O3[M+Na]+487.0210, found: 487.0210.

[0171] 7c: White solid, yield: 73%, m.p. 87-89 °C. 1 H NMR (400 MHz, CDCI3) δ 8.85 (dd, J = 2.0, 0.9 Hz, 1 H), 8.07 (dd, J = 1.9, 0.7 Hz, 1 H), 7.52 (d, J = 6.8 Hz, 1 H), 7.37 (d, J = 9.0 Hz, 1 H), 5.48 (t, J = 8.3 Hz, 1 H), 3.89 - 3.74 (m, 2 H), 2.79 - 2.61 (m, 2 H), 2.27 - 2.13 (m, 1 H), 1.22 (dd, J = 7.0, 2.2 Hz, 6 H). 13 C NMR (101 MHz, CDCI3) δ 176.5, 170.2, 158.5 (d, J = 255.8 Hz), 154.5, 144.3 (q, J = 4.0 Hz), 134.9 (q, J = 3.6 Hz), 134.6 (d, J = 10.8 Hz), 132.3 (d, J = 3.9 Hz), 132.3, 131.7 (d, J = 4.3 Hz), 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.4 Hz), 122.5 (q, J = 273.1 Hz), 118.4 (d, J = 26.1 Hz), 70.2, 46.4, 33.8, 26.8, 19.0, 18.8. HRMS (ESI): calcd for C 20 H 16 Cl2F4N2O3[M+Na]+501.0366, found: 501.0364.

[0172] 7d: yellowish solid, yield: 65%, m.p. 112-114 °C. 1 H NMR (400 MHz, CDC13) δ 8.84 (dd, J = 2.0, 1.0 Hz, 1H), 8.06 (dd, J = 1.9, 0.8 Hz, 1H), 7.52 (d, J = 6.9 Hz, 1H), 5.46 (t, J = 8.2 Hz, 1H), 3.88-3.75 (m, 2H), 2.76-2.64 (m, 1H), 2.26-2.12 (m, 1H), 1.26 (s, 10H). 13 C NMR (101 MHz, CDC13) δ 177.8, 170.2, 158.5 (d, J = 255.8 Hz), 154.5, 144.3 (q, J = 4.1 Hz), 134.9 (q, J = 3.7 Hz), 134.6 (d, J = 10.8 Hz), 132.3 (d, J = 4.3 Hz), 132.3, 131.7 (d, J = 4.4 Hz), 127.4 (q, J = 33.8 Hz), 125.2 (d, J = 16.5 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 70.2, 46.3, 38.8, 27.1, 26.7. HRMS (ESI): calcd for C 21 H 18 Cl2F4N2O3[M+Na]+515.0523, found: 515.0508.

[0173] 7e: white solid, yield: 86%, m.p. 61-63 °C. 1 H NMR (400 MHz, CDC13) δ 8.86 (dd, J = 2.0, 0.9 Hz, 1H), 8.15-8.05 (m, 3H), 7.63-7.54 (m, 2H), 7.50-7.42 (m, 2H), 7.39 (d, J = 9.1 Hz, 1H), 5.70 (t, J = 8.2 Hz, 1H), 3.97-3.81 (m, 2H), 2.92-2.80 (m, 1H), 2.43-2.29 (m, 1H). 13 C NMR(101 MHz, CDCI3) δ 170.1, 165.9, 158.6 (d, J = 255.9 Hz), 154.5, 144.3 (q, J = 4.0 Hz), 134.9 (q, J = 3.6 Hz), 134.7 (d, J = 10.7 Hz), 133.5, 132.3 (d, J = 3.9 Hz), 132.3, 131.7 (d, J = 4.4 Hz), 130.0, 129.3, 128.4, 127.4 (q, J = 33.9 Hz), 125.3 (d, J = 16.5 Hz), 122.5 (q, J = 273.2 Hz), 1 18.4 (d, J = 26.2 Hz), 71.1, 46.5, 27.0. HRMS (ESI): calcd for C 23 H 14 Cl2F4N2O3[M + Na]+ 535.0210, found: 535.0209.

[0174] 7f: colorless viscous liquid, yield: 80%. 1 H NMR (400 MHz, CDCI3) δ 8.88-8.83 (m, 1 H), 8.12-8.02 (m, 3H), 7.56 (d, J = 6.8 Hz, 1 H), 7.39 (d, J = 9.0 Hz, 1 H), 6.97-6.88 (m, 2H), 5.66 (t, J = 8.2 Hz, 1 H), 3.95-3.80 (m, 5H), 2.91-2.78 (m, 1 H), 2.41-2.27 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 170.3, 165.6, 163.8, 158.6 (d, J = 255.9 Hz), 154.5, 144.3 (q, J = 3.8 Hz), 134.9 (q, J = 3.6 Hz), 134.7 (d, J = 10.8 Hz), 132.4 (d, J = 3.8 Hz), 132.3, 132.1, 131.7 (d, J = 4.4 Hz), 127.4 (q, J = 33.9 Hz), 125.2 (d, J = 16.3 Hz), 122.5 (q, J = 273.5 Hz), 121.7, 1 18.4 (d, J = 26.1 Hz), 1 13.7, 70.8, 55.5, 46.5, 27.1. HRMS (ESI): calcd for C 24 H 16 Cl2F4N2O4[M + Na]+ 565.0315, found: 565.0313.

[0175] 7g: colorless viscous liquid, yield: 83%. 1 H NMR(400 MHz, CDCI3) δ 8.78 (dd, J = 2.0, 0.9 Hz, 1 H), 8.09 - 8.03 (m, 2 H), 8.03 - 7.97 (m, 1 H), 7.48 (d, J = 6.8 Hz, 1 H), 7.32 (d, J = 9.0 Hz, 1 H), 7.10 - 6.99 (m, 2 H), 5.62 (t, J = 8.3 Hz, 1 H), 3.89 - 3.73 (m, 2 H), 2.84 - 2.72 (m, 1 H), 2.35 - 2.21 (m, 1 H). 13 C NMR (101 MHz, CDCI3) δ 170.0, 166.1 (d, J = 254.8 Hz), 164.9, 158.6 (d, J = 256.1 Hz), 154.4, 144.3 (q, J = 3.9 Hz), 134.9 (q, J = 3.7 Hz), 134.6 (d, J = 10.7 Hz), 132.6 (d, J = 9.4 Hz), 132.3, 132.2 (d, J = 3.6 Hz), 131.7 (d, J = 4.5 Hz), 127.4 (q, J = 33.8 Hz), 125.5 (d, J = 3.0 Hz), 125.3 (d, J = 16.4 Hz), 122.5 (q, J = 273.3 Hz), 118.4 (d, J = 26.3 Hz), 115.7 (d, J = 22.0 Hz), 71.2, 46.4, 26.9. 19 F NMR (376 MHz, CDCI3) δ -62.3, -104.6, -109.5. HRMS (ESI): calcd for C 23 H 13 Cl2F5N2O3[M+Na]+553.0116, found: 553.0116.

[0176] 7h: white solid, yield: 82%, melting point: 128-130 °C. 1 H NMR (400 MHz, CDCI3) δ 8.85 (dd, J = 2.0, 0.9 Hz, 1 H), 8.07 (dd, J = 2.0, 0.8 Hz, 1 H), 7.50 (d, J = 6.8 Hz, 1 H), 7.40 - 7.26 (m, 6 H), 5.49 (t, J = 8.3 Hz, 1 H), 3.86 - 3.68 (m, 4 H), 2.77 - 2.64 (m, 1 H), 2.25 - 2.11 (m, 1 H). 13 C NMR(101 MHz, CDCI3) δ 170.9, 169.9, 158.6 (d, J = 255.9 Hz), 154.5, 144.3 (q, J = 3.9 Hz), 134.9 (q, J = 3.6 Hz), 134.6 (d, J = 10.8 Hz), 133.4, 132.3, 132.2 (d, J = 3.8 Hz), 131.6 (d, J = 4.5 Hz), 129.3, 128.6, 127.6 (q, J = 33.9 Hz), 127.3, 125.2 (d, J = 16.4 Hz), 122.5 (q, J = 273.2 Hz), 118.4 (d, J = 26.2 Hz), 70.9, 46.4, 40.9, 26.7. HRMS (ESI): calcd for C 24 H 16 Cl2F4N2O3[M+Na]+549.0366, found: 549.0365.

[0177] Example 2

[0178] The post-emergence herbicidal activity of the target compounds against Amaranthus retroflexus, Abutilon theophrasti, Medicago sativa, Echinochloa crus-galli, Digitaria sanguinalis and Lolium multiflorum is shown in Table 2.

[0179] The post-emergence herbicidal activity was determined by spraying three representative grass weeds, Echinochloa crus-galli, Digitaria sanguinalis and Lolium multiflorum, and three representative broadleaf weeds, Abutilon theophrasti, Amaranthus retroflexus and Medicago sativa. The PPO herbicides, flumioxazin and acifluorfen, which have a broad spectrum of herbicidal activity, were used as positive controls. The target compounds were dissolved in N,N-dimethylformamide to prepare a high concentration stock solution, which was then diluted with 0.1% Tween-80 water to the desired concentration. The spraying dose (active ingredient, g ai / ha) was calculated by dividing the mass of the spraying inhibitor by the upper surface area of the pot. Pots with a diameter of 7 cm were selected before planting, and about 6-10 seeds of the weed were sown, and covered with 0.5 cm of soil. During the experiment, the temperature in the greenhouse was maintained at 25-28°C, and the air humidity was maintained at about 50-75%. The post-emergence herbicidal activity was determined by treating the 2-3 leaf stage of the monocotyledonous and broadleaf weeds with the diluted inhibitor emulsion, and using the solvent without the inhibitor (N,N-dimethylformamide + Tween-80) as a negative control. Each treatment was repeated three times. The results of the herbicidal activity were evaluated by visual observation 14 days after the treatment,

[0180] Table 2 Post-emergence herbicidal activity of pyrrolidinone-containing 2-phenylpyridine derivatives

[0181]

[0182]

[0183]

[0184] As shown in Table 2, all compounds showed 100% inhibition of A. retroflexus at the 150 g / ha dose, but showed significant differences in inhibition of A. crispus, M. officinalis, and the three grass weeds. Compound 4 showed significantly better herbicidal activity than compound 7. Therefore, compound 4 was further tested for herbicidal activity at 75 and 37.5 g / ha. The results showed that at 37.5 g ai / ha, compounds 4d, 4f, and 41 showed more than 80% inhibition of the three broadleaf weeds and 30-80% inhibition of the three grass weeds. At 18.75 and 9.375 g ai / ha, compounds 4d, 4f, and 41 showed better herbicidal activity than the positive control of acifluorfen. Compounds 4d and 41 showed 100% inhibition of A. retroflexus and A. crispus, which was better than the positive control of acifluorfen (100%, 10%). Compound 41 showed 60% inhibition of D. sanguinalis, which was better than the positive control of acifluorfen (50%). Compound 41 showed high herbicidal activity at low doses, but was lower than the positive control of clopyralid.

[0185] Example 3

[0186] Crop safety testing of target compounds

[0187] Safety evaluations were performed on six crops, wheat, rice, peanut, corn, soybean, and cotton, using the greenhouse spray method of Example 2 at application rates of 37.5-150 g ai / ha.

[0188] Table 3 Post-emergence crop selectivity of pyrrolidinone-containing 2-phenylpyridine derivatives

[0189]

[0190] As shown in Table 3, compounds 4d, 4f, and 41 showed high sensitivity to peanut, soybean, and cotton at 150, 75, and 37.5 g ai / ha. In contrast, these compounds showed low sensitivity to rice and corn at 75 and 37.5 g ai / ha, which was significantly lower than clopyralid. Compound 4f showed low sensitivity to wheat at 75 g ai / ha, which was significantly lower than clopyralid. These findings indicate that compounds 4d, 4f, and 41 can be used as potential herbicides for controlling broadleaf weeds and some grasses in rice, corn, and wheat fields at 75 and 37.5 g ai / ha.

[0191] Although the above embodiments have been described in detail, it should be understood that these are only some embodiments of the present application, but not all embodiments. Other embodiments can be obtained on the basis of the above embodiments without creativity, and these embodiments all belong to the protection scope of the present application.

Claims

1. A pyrrolidinone-containing 2-phenylpyridine derivative, characterized by, The structure general formula of the pyrrolidone-containing 2-phenylpyridine derivative is shown as formula I or formula II: X is selected from oxygen or NH; R 1 any one selected from the group consisting of C1-C6alkyl, phenyl-C1-C4alkyl, C3-C6alkynyl, C1-C6haloalkyl, C1-C6alkylcarbonyl-C1-C6alkyl; R 2 is selected from any one of C1-C6alkyl, phenyl, phenyl-C1-C4alkyl.

2. A method of synthesizing a pyrrolidinone-containing 2-phenylpyridine derivative according to claim 1, characterized by, The structure general formula of the pyrrolidone-containing 2-phenylpyridine derivative is shown as formula I, and the steps are as follows: 1) condensation reaction of the compound shown as formula III with compound 1 to obtain compound 2; The temperature of the condensation reaction is 50-80 DEG C, and the time is 6-12 hours; The structures of the compounds 1 and 2 are as follows: 2) acylation reaction of compound 2 with oxalyl chloride under catalysis of N,N-dimethylformamide to obtain compound 3; The temperature of the acylation reaction is 25-40 DEG C, and the time is 2-6 hours; The structure of the compound 3 is as follows: 3) substitution reaction of compound 3 with different substituted alcohols or amines under action of triethylamine to obtain the compound shown as formula I; The temperature of the substitution reaction is 25-40 DEG C, and the time is 2-6 hours; The structure of the compound shown as formula I is as follows:

3. The method of synthesis of claim 2, wherein, The molar ratio of the compound shown as formula III to compound 1 in the step 1) is 1-5; The solvent used in the condensation reaction is one or more of acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, tetrahydrofuran and dichloromethane; The molar ratio of oxalyl chloride to compound 2 is 1-3; the solvent used in the acylation reaction is one or more of dichloromethane, dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile, chloroform and chlorobenzene; The catalyst used in the acylation reaction is one or more of dimethyl sulfoxide, N,N-dimethylformamide, acetonitrile and pyridine; The acid-binding agent used in the substitution reaction of the step 3) is one or more of pyridine, triethylamine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; The molar ratio of the base to compound 3 in the substitution reaction is 1-3; The solvent used in the substitution reaction is one or more of dichloromethane, diethyl ether, carbon tetrachloride, toluene and benzene; The molar ratio of the different substituted alcohols or amines to compound 3 in the substitution reaction is 1-3.

4. A method of synthesizing the pyrrolidinone-containing 2-phenylpyridine derivative of claim 1, characterized by, The structure general formula of the pyrrolidone-containing 2-phenylpyridine derivative is shown as formula II, comprising the following steps: A, substitution reaction of compound 1 with the compound shown as formula IV under action of trimethylaluminum to obtain compound 5; The temperature of the substitution reaction is 0-30 DEG C, and the time is 4-8 hours; The structures of the compounds 1 and 5 are as follows: B, substitution reaction of compound 5 with 1,8-diazabicyclo[5,4,0]undec-7-ene after generating a bromide intermediate under action of triphenylphosphine and carbon tetrabromide to obtain compound 6; The temperature of the substitution reaction is 0-30 DEG C, and the time is 4-8 hours; The structure of the compound 6 is as follows: C, substitution reaction of compound 6 with different substituted acyl chlorides under action of triethylamine to obtain the compound shown as formula II; The temperature of the substitution reaction is 25-40 DEG C, and the time is 2-6 hours; The structure of the compound shown as formula II is as follows:

5. The method of synthesis of claim 4, wherein, The molar ratio of the compound shown as formula IV to compound 1 in the step A is 1-3. The molar ratio of the trimethylaluminum to the compound 1 is 1 to 3; The molar ratio of the triphenylphosphine to the compound 5 in the step B is 1 to 3; The molar ratio of the carbon tetrabromide to the compound 5 is 1 to 3; The molar ratio of the 1,8-diazabicyclo[5,4,0]undec-7-ene to the intermediate bromide is 1 to 3; The acid binding agent used in the substitution reaction in the step C is one or more of pyridine, triethylamine, sodium carbonate, sodium bicarbonate, potassium carbonate, sodium hydroxide and potassium hydroxide; The molar ratio of the base to the compound 6 in the substitution reaction is 1 to 3; The solvent used in the substitution reaction is one or more of dichloromethane, diethyl ether, carbon tetrachloride, toluene and benzene; The molar ratio of the different substituted acyl chloride to the compound 6 in the substitution reaction is 1 to 3.

6. Use of the pyrrolidinone-containing 2-phenylpyridine derivative of claim 1 in controlling weeds. The weeds are one or more of Amaranthus retroflexus, Abutilon theophrasti, Medicago sativa, Echinochloa crus-galli, Digitaria sanguinalis and Lolium multiflorum.

7. Use according to claim 6, characterized in that, The pyrrolidinone-containing 2-phenylpyridine derivative is used in an amount of 9.375 to 150 g ai / ha.

8. Use according to claim 6 or 7, characterized in that, The pyrrolidinone-containing 2-phenylpyridine derivative is used in an amount of 37.5 to 75 g ai / ha.

9. A herbicide, characterized by, The pyrrolidinone-containing 2-phenylpyridine derivative of claim 1 is included.

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