Tetrahydrocinnamomum camphora derivative containing sulfonamide fragment as well as preparation method and application of tetrahydrocinnamomum camphora derivative

Abstract

The invention discloses a tetrahydrocinnamomum camphora derivative containing a sulfonamide fragment as well as a preparation method and application of the tetrahydrocinnamomum camphora derivative. The compound has a structure as shown in a formula I, and can be prepared from tetrahydrolinalool or tetrahydrolinalool through oxidative chlorination and ammoniation reaction. The method disclosed by the invention is simple and convenient to operate, mild in condition and high in yield, and the prepared tetrahydrolinalool compound containing the sulfonamide fragment has excellent herbicidal activity and can be used for preventing and treating agricultural weeds. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of agricultural herbicides, and specifically relates to a tetrahydrocinnamic acid derivative containing a sulfonamide fragment, a preparation method thereof, and use thereof as a herbicide Background Art

[0002] Tetrahydrocinnamate derivatives have multiple biological activities and are widely used in medicine, agriculture and other fields. Based on the principle of active substructure splicing, the present invention designs and synthesizes a tetrahydrocinnamate derivative containing a sulfonamide fragment. Combined with the bioassay experimental data, it is concluded that the compound has excellent herbicidal activity and can be used to prevent agricultural weeds.

[0003] The tetrahydrocinnamic acid derivative containing sulfonamide fragments described in the present invention has not been reported in the prior art. Summary of the invention

[0004] The purpose of the present invention is to provide a tetrahydrocinnamic acid derivative containing a sulfonamide fragment, a preparation method thereof and use thereof as a herbicide, so as to meet the new requirements for herbicides that are constantly put forward in agriculture.

[0005] To achieve the above object, the technical solution of the present invention is as follows:

[0006] The present invention provides a tetrahydrocinnamic acid derivative containing a sulfonamide fragment, the structure of which is shown in Formula I:

[0007]

[0008] Where: Selected from

[0009] n is 0 or 1.

[0010] The present invention provides a preparation route of a tetrahydrocinnamic acid derivative I containing a sulfonamide fragment, and the reaction formula thereof is as follows:

[0011]

[0012] The specific preparation method comprises the following steps:

[0013] Step 1: an oxidizing agent, a chlorinating agent and a compound II are mixed in a solvent to undergo an oxidative chlorination reaction for 1 to 3 hours; wherein the compound II is tetrahydrolinalool (n in formula II is 0) or tetrahydrolinaloolmethyl mercaptan (n in formula II is 1);

[0014] Step 2: Add appropriate base and amine compounds to the reaction system of step 1 An amination reaction takes place for 2 to 5 hours, and after post-treatment, compound I is obtained, which is a tetrahydrocinnamic acid derivative containing a sulfonamide fragment.

[0015] Preferably, the solvent in step 1 is selected from any one of acetonitrile, tetrahydrofuran, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, dichloromethane or toluene.

[0016] Preferably, in step 1, the oxidant is selected from any one of m-chloroperbenzoic acid, hydrogen peroxide, sodium hypochlorite, sodium periodate or diacetoxy iodobenzene. The molar ratio of the oxidant to compound II is (3-5):1.

[0017] Preferably, the chlorination agent in step 1 is selected from any one of m-dichlorothionyl, oxalyl chloride or N-chlorosuccinimide. The molar ratio of the chlorination agent to compound II is (1-1.5):1.

[0018] Preferably, the appropriate temperature in step 1 is 25-50°C.

[0019] Preferably, the appropriate base in step 2 is selected from any one of trimethylamine, triethylamine or pyridine. The amount of the base and compound II is such that 1 mmol of compound II corresponds to 0.5-1 ml of the base.

[0020] Preferably, the amine compound in step 2 In the structure The substituents are defined the same as those in the aforementioned compound I. The molar ratio of the amine compound to the compound II is (0.8-1):1.

[0021] Preferably, the amine compound is methylamine, methyl carbamate, dimethylamine, diethylamine, dipropylamine, piperidine, pyrrole, morpholine, 1-(2-pyrimidinyl)piperazine, aniline, 4-methoxyaniline, 4-chloroaniline, 4-fluoroaniline, 4-trifluoromethylaniline, 4-trifluorothiomethylaniline, 3-chloroaniline, 3-fluoroaniline, 3-trifluoromethylaniline, 3-trifluorothiomethylaniline, 3,5-dichloroaniline or 2-aminothiophene.

[0022] Preferably, the appropriate temperature in step 2 is 25-50°C.

[0023] The present invention provides the use of tetrahydrocinnamic acid derivatives containing sulfonamide fragments of compounds shown in formula I as herbicides.

[0024] The technical effects achieved by the present invention are:

[0025] 1. The preparation method of the compound provided by the present invention is simple, the reaction conditions are mild, and the yield is high;

[0026] 2. The tetrahydrocinnamic acid derivative containing sulfonamide fragment provided by the present invention has a novel structure and has a good inhibitory effect on the growth of monocotyledonous weeds or dicotyledonous weeds such as crabgrass, barnyard grass, quinoa, shepherd's purse and the like. At the same time, the use dosage is low, the herbicidal activity is high, the cost is reduced, and the pollution to the environment is reduced, showing a good prospect for development and utilization. DETAILED DESCRIPTION

[0027] The present invention is further illustrated below in conjunction with specific examples. It should be understood that these examples are only used to illustrate the present invention and do not limit the scope of the present invention. After reading the present invention, modifications of various equivalent forms of the present invention by those skilled in the art all fall within the scope defined by the appended claims of the present application. The specific compounds of formula I listed in Table 1 can be used to illustrate the present invention, but do not limit the present invention.

[0028] Table 1

[0029]

[0030]

[0031]

[0032] Example 1: Preparation of Compound I-1

[0033] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol) (purchased from Shanghai Haoyuan Pharmaceutical Co., Ltd.), m-chloroperbenzoic acid (1.04 g, 6 mmol), dichlorothionyl (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25° C. for 3 hours.

[0034] Step 2: Add ammonia water (0.39 ml, 2 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 25°C for 5 hours, add 20 ml of saturated ammonium chloride solution, extract with ethyl acetate (15 ml x 3), wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-1, with a yield of 81% and a product content of 98.1%.

[0035] Example 2: Preparation of Compound I-2

[0036] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), oxalyl chloride (0.26 ml, 3 mmol) and 25 mL of tetrahydrofuran into a reaction flask and stir at 40° C. for 2 hours.

[0037] Step 2: Add methylamine aqueous solution (0.18 ml, 1.6 mmol) and trimethylamine (2 ml) to the reaction system of step 1, stir at 40°C for 3 hours, add 20 ml of saturated ammonium chloride solution, extract with ethyl acetate (15 ml x 3), wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-2, with a yield of 79% and a product content of 98.3%.

[0038] Example 3: Preparation of Compound I-3

[0039] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), sodium hypochlorite (0.74 g, 10 mmol), N-chlorosuccinimide (0.32 g, 2.4 mmol) and 25 mL of dioxane into a reaction flask and stir at 50° C. for 1 hour.

[0040] Step 2: Add methyl carbamate (0.14 g, 1.8 mmol) and triethylamine (1.6 ml) to the reaction system of step 1, stir at 50°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-3 with a yield of 83% and a product content of 97.9%.

[0041] Example 4: Preparation of Compound I-4

[0042] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), sodium periodate (1.30 g, 6 mmol), N-chlorosuccinimide (0.37 g, 2.8 mmol) and 25 mL of dimethyl sulfoxide into a reaction flask and stir at 50° C. for 1 hour.

[0043] Step 2: Add dimethylamine (0.10 ml, 2 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 50°C for 2 hours, add 20 ml of saturated ammonium chloride solution, extract with ethyl acetate (15 ml x 3), wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-4 with a yield of 77% and a product content of 97.9%.

[0044] Example 5: Preparation of Compound I-5

[0045] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), diacetoxyiodobenzene (1.90 g, 6 mmol), N-chlorosuccinimide (0.26 g, 2 mmol) and 25 mL of dichloromethane into a reaction flask and stir at 25° C. for 2 hours.

[0046] Step 2: Add diethylamine (0.12 g, 1.6 mmol) and pyridine (1.2 ml) to the reaction system of step 1, stir at 25°C for 5 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-5 with a yield of 80% and a product content of 98.2%.

[0047] Example 6: Preparation of Compound I-6

[0048] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), m-chloroperbenzoic acid (1.04 g, 6 mmol), N-chlorosuccinimide (0.26 g, 2 mmol), and 25 mL of N,N-dimethylformamide into a reaction flask, and stir at 40° C. for 2 hours;

[0049] Step 2: Add dipropylamine (0.20 g, 2 mmol) and pyridine (1.4 ml) to the reaction system of step 1, stir at 40°C for 3 hours, add 20 mL of saturated ammonium chloride solution, extract with ethyl acetate (15 mL x 3), wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-6, with a yield of 78% and a product content of 98.1%.

[0050] Example 7: Preparation of Compound I-7

[0051] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), m-chloroperbenzoic acid (1.04 g, 6 mmol), dichlorothionyl (0.14 ml, 2 mmol) and 25 mL of toluene into a reaction flask and stir at 50° C. for 1 hour.

[0052] Step 2: Add hexahydropiperidine (0.14 g, 1.6 mmol) and pyridine (1.8 ml) to the reaction system of step 1, stir at 50°C for 4 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-7 with a yield of 74% and a product content of 97.7%.

[0053] Example 8: Preparation of Compound I-8

[0054] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), m-chloroperbenzoic acid (1.04 g, 6 mmol), dichlorothionyl (0.14 ml, 2 mmol) and 25 mL of toluene into a reaction flask and stir at 50° C. for 1 hour.

[0055] Step 2: Add tetrahydropyrrole (0.11 g, 1.6 mmol) and pyridine (1.8 ml) to the reaction system of step 1, stir at 50°C for 4 hours, add 20 mL of saturated ammonium chloride solution, extract with ethyl acetate (15 mL x 3), wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-8 with a yield of 77% and a product content of 97.8%.

[0056] Example 9: Preparation of Compound I-9

[0057] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), m-chloroperbenzoic acid (1.04 g, 6 mmol), dichlorothionyl (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 50° C. for 1 hour.

[0058] Step 2: Add morpholine (0.14 g, 1.6 mmol) and pyridine (2 ml) to the reaction system of step 1, stir at 50°C for 4 hours, add 20 mL of saturated ammonium chloride solution, extract with ethyl acetate (15 mL x 3), wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-8 with a yield of 77% and a product content of 97.8%.

[0059] Example 9: Preparation of Compound I-9

[0060] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), m-chloroperbenzoic acid (1.04 g, 6 mmol), dichlorothionyl (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 50° C. for 1 hour.

[0061] Step 2: Add 1-(2-pyrimidinyl)piperazine (0.26 g, 1.6 mmol) and pyridine (2 ml) to the reaction system of step 1, stir at 50°C for 4 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-9 with a yield of 75% and a product content of 98.2%.

[0062] Example 10: Preparation of Compound I-10

[0063] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), m-chloroperbenzoic acid (1.04 g, 6 mmol), dichlorothionyl (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 50° C. for 1 hour.

[0064] Step 2: Add 1-(2-pyrimidinyl)piperazine (0.99 g, 1.6 mmol) and pyridine (2 ml) to the reaction system of step 1, stir at 50°C for 4 hours, add 20 mL of saturated ammonium chloride solution, extract with ethyl acetate (15 mL x 3), wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-10 with a yield of 78% and a product content of 97.5%.

[0065] Example 11: Preparation of Compound I-11

[0066] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 25° C. for 2 hours.

[0067] Step 2: Add aniline (0.15 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 25°C for 3 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-11 with a yield of 83% and a product content of 98.5%.

[0068] Example 12: Preparation of Compound I-12

[0069] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 25° C. for 2 hours.

[0070] Step 2: Add 4-methoxyaniline (0.99 g, 1.6 mmol) and triethylamine (1 ml) to the reaction system of step 1, stir at 25°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-12 with a yield of 81% and a product content of 98.3%.

[0071] Example 13: Preparation of Compound I-13

[0072] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 25° C. for 2 hours.

[0073] Step 2: Add 4-chloroaniline (0.20 g, 1.6 mmol) and triethylamine (1 ml) to the reaction system of step 1, stir at 25°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-13 with a yield of 79% and a product content of 98.2%.

[0074] Example 14: Preparation of Compound I-14

[0075] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0076] Step 2: Add 4-fluoroaniline (0.18 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 25°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-14 with a yield of 81% and a product content of 97.8%.

[0077] Example 15: Preparation of Compound I-15

[0078] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0079] Step 2: Add 4-trifluoromethylaniline (0.26 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 40°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-15 with a yield of 77% and a product content of 97.6%.

[0080] Example 16: Preparation of Compound I-16

[0081] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0082] Step 2: Add 4-trifluorothiomethylaniline (0.31 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 50°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-16 with a yield of 76% and a product content of 98.1%.

[0083] Example 17: Preparation of Compound I-17

[0084] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0085] Step 2: Add 3-chloroaniline (0.20 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 50°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-17 with a yield of 79% and a product content of 97.7%.

[0086] Example 18: Preparation of Compound I-18

[0087] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0088] Step 2: Add 3-fluoroaniline (0.26 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 25°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-18 with a yield of 81% and a product content of 98.4%.

[0089] Example 19: Preparation of Compound I-19

[0090] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0091] Step 2: Add 3-trifluoromethylaniline (0.26 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 25°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-19 with a yield of 75% and a product content of 97.5%.

[0092] Example 20: Preparation of Compound I-20

[0093] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0094] Step 2: Add 3-trifluorothiomethylaniline (0.31 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 50°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-20 with a yield of 72% and a product content of 98.3%.

[0095] Example 21: Preparation of Compound I-21

[0096] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol), and 25 mL of acetonitrile into a reaction bottle and stir at 25 °C for 2 hours;

[0097] Step 2: Add 3,5-dichloroaniline (0.26 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 25°C for 3 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-21 with a yield of 82% and a product content of 97.8%.

[0098] Example 22: Preparation of Compound I-22

[0099] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 25° C. for 2 hours.

[0100] Step 2: Add 3,5-dichloroaniline (0.21 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 50°C for 3 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-22 with a yield of 71% and a product content of 97.2%.

[0101] Example 23: Preparation of Compound I-23

[0102] Step 1: Add tetrahydrolinalethiol (0.35 g, 2 mmol), hydrogen peroxide (0.8 ml, 8 mmol), thionyl chloride (0.14 ml, 2 mmol) and 25 mL of acetonitrile into a reaction bottle and stir at 25° C. for 2 hours.

[0103] Step 2: Add 2-aminothiophene (0.16 g, 1.6 mmol) and pyridine (1 ml) to the reaction system of step 1, stir at 25°C for 2 hours, add 20 mL of saturated ammonium chloride solution, and extract with ethyl acetate (15 mL x 3). Wash with saturated brine, dry over anhydrous sodium sulfate, concentrate under reduced pressure, and separate by column chromatography to obtain compound I-23 with a yield of 80% and a product content of 98.4%.

[0104] Example 24: Preparation of Compound I-24

[0105] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol) (purchased from Shanghai Haoyuan Pharmaceutical Co., Ltd.), the other operation process was the same as Example 1 to obtain compound I-24 with a yield of 73% and a product content of 97.8%.

[0106] Example 25: Preparation of Compound I-25

[0107] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operations were the same as in Example 2 to obtain compound I-25 with a yield of 76% and a product content of 98.1%.

[0108] Example 26: Preparation of Compound I-26

[0109] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 3 to obtain compound I-26 with a yield of 75% and a product content of 98.3%.

[0110] Example 27: Preparation of Compound I-27

[0111] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operations were the same as in Example 4 to obtain compound Ⅰ-27 with a yield of 79% and a product content of 98.2%.

[0112] Example 28: Preparation of Compound I-27

[0113] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operations were the same as in Example 5 to obtain compound I-28 with a yield of 77% and a product content of 98.5%.

[0114] Example 29: Preparation of Compound I-29

[0115] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operations were the same as in Example 6 to obtain compound I-29 with a yield of 81% and a product content of 98.4%.

[0116] Example 30: Preparation of Compound I-30

[0117] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operations were the same as in Example 7 to obtain compound Ⅰ-30 with a yield of 78% and a product content of 97.9%.

[0118] Example 31: Preparation of Compound I-31

[0119] Except that the raw material was tetrahydrocinnamate (0.38 g, 2 mmol), the other operations were the same as in Example 8 to obtain compound I-30 with a yield of 76% and a product content of 98.1%.

[0120] Example 32: Preparation of Compound I-32

[0121] Except that the raw material was tetrahydrocinnamate (0.38 g, 2 mmol), the other operation process was the same as Example 9 to obtain compound I-32 with a yield of 74% and a product content of 98.5%.

[0122] Example 33: Preparation of Compound I-33

[0123] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 10 to obtain compound I-33 with a yield of 77% and a product content of 98.2%.

[0124] Example 34: Preparation of Compound I-34

[0125] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 11 to obtain compound I-34 with a yield of 80% and a product content of 98.4%.

[0126] Example 35: Preparation of Compound I-34

[0127] Except that the raw material was tetrahydrocinnamate (0.38 g, 2 mmol), the other operation process was the same as Example 12 to obtain compound I-35 with a yield of 81% and a product content of 97.8%.

[0128] Example 36: Preparation of Compound I-36

[0129] Except that the raw material was tetrahydrocinnamate (0.38 g, 2 mmol), the other operation process was the same as Example 13 to obtain compound I-36 with a yield of 79% and a product content of 98.0%.

[0130] Example 37: Preparation of Compound I-37

[0131] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 14 to obtain compound I-37 with a yield of 82% and a product content of 98.5%.

[0132] Example 38: Preparation of Compound I-38

[0133] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 15 to obtain compound I-38 with a yield of 81% and a product content of 98.3%.

[0134] Example 39: Preparation of Compound I-39

[0135] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 16 to obtain compound I-39 with a yield of 78% and a product content of 97.6%.

[0136] Example 40: Preparation of Compound I-40

[0137] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operations were the same as Example 17 to obtain compound Ⅰ-40 with a yield of 80% and a product content of 98.2%.

[0138] Example 41: Preparation of Compound I-41

[0139] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 18 to obtain compound Ⅰ-41 with a yield of 83% and a product content of 98.6%.

[0140] Example 42: Preparation of Compound I-42

[0141] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 19 to obtain compound Ⅰ-42 with a yield of 82% and a product content of 98.3%.

[0142] Example 43: Preparation of Compound I-43

[0143] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 20 to obtain compound Ⅰ-43 with a yield of 81% and a product content of 98.1%.

[0144] Example 44: Preparation of Compound I-44

[0145] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 21 to obtain compound Ⅰ-44 with a yield of 79% and a product content of 98.2%.

[0146] Example 45: Preparation of Compound I-45

[0147] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 22 to obtain compound Ⅰ-45 with a yield of 82% and a product content of 97.7%.

[0148] Example 46: Preparation of Compound I-46

[0149] Except that the raw material was tetrahydrocinnamyl mercaptan (0.38 g, 2 mmol), the other operation process was the same as Example 23 to obtain compound Ⅰ-46 with a yield of 75% and a product content of 98.1%.

[0150] Representative compounds in each series 1 H NMR and HRMS data are as follows:

[0151] Compound I-3: 1 H NMR (400MHz, CDCl3) δ (ppm) 3.81 (s, 3H), 1.96-1.87 (m, 2H), 1.81-1.74 (m, 1H), 1.67-1.61 (m, 1H), 1.53-1.45 (m, 2H), 1.40 -1.31(m,5H),1.24-1.17(m,1H),0.91(t,J=7.2Hz,3H),0.84(d,J=6.7Hz,3H),0.79(d,J=6.6Hz,3H); HRMS(ESI)m / z:calcd for C 12 H 26 NO4S[M+H] + 208.1578 found 208.1574.

[0152] Compound I-1: 1 H NMR (400MHz, CDCl3) δ (ppm) 8.33 (d, J = 3.6 Hz, 2H), 6.52 (t, J = 3.3 Hz, 1H), 3.76-3.71 (m, 2H), 3.63-3.58 (m, 2H), 3.12-3.09 (m, 4H), 1.96-1.79 (m, 3H) ,1.75-1.70(m,1H),1.53-1.43(m,2H),1.37-1.20(m,6H),0.95(t,J=7.1Hz,3H),0.84(d,J=6.8Hz,3H),0.77(d,J=6.5Hz,3H); HRMS(ESI)m / z:calcd for C 18 H 33 N4O2S[M+H] + 369.2319 found 369.2317.

[0153] Compound I-12: 1 H NMR(400MHz, CDCl3)δ(ppm)8.95(s,1H),7.15-7.11(m,2H),6.91-6.86(m,2H),3.78(s,3H),1.99-1.84(m,3H),1.74-1.69(m,1H) ,1.52-1.32(m,7H),1.26-1.20(m,1H),0.91(t,J=7.0Hz,3H),0.86(d,J=6.8Hz,3H),0.80(d,J=6.7Hz,3H); HRMS(ESI)m / z:calcd for C 17 H 30 NO3S[M+H] + 328.1941 found 328.1938.

[0154] Compound I-15: 1 H NMR (400MHz, CDCl3) δ (ppm) 8.92 (s, 1H), 7.61-7.58 (m, 2H), 7.23-7.17 (m, 2H), 1.95-1.82 (m, 3H), 1.76-1.71 (m, 1H), 1.63-1.45 (m, 6H),1.39-1.31(m,1H),1.23-1.19(m,1H),0.93(t,J=7.2Hz,3H),0.82(d,J=6.7Hz,3H),0.76(d,J=6.7Hz,3H); HRMS(ESI)m / z:calcd for C 17 H30 NO3S[M+H] + 366.1710 found 366.1708.

[0155] Compound I-21: 1 H NMR (400MHz, CDCl3) δ (ppm) 7.99 (s, 1H), 7.24 (d, J = 8.0 Hz, 2H), 7.08-7.00 (m, 1H), 1.99-1.92 (m, 1H), 1.90-1.79 (m, 2H), 1.73 (dt, J =11.7,6.2Hz,1H),1.58-1.32(m,7H),1.30-1.20(m,1H),0.93(t,J=7.2Hz,3H),0.82(dd,J=25.0,6.7Hz,6H); HRMS(ESI)m / z:calcd for C 16 H 26 Cl2NO2S[M+H] + 366.1056 found 366.1053.

[0156] Compound I-32: 1 H NMR (400MHz, CDCl3) δ (ppm) 3.70 (ddd, J = 6.6, 5.6, 0.9Hz, 4H), 3.44 (d, J = 14.8Hz, 1H), 3.26-3.17 (m, 3H), 3.16-3.07 ( m,2H),1.64-1.55(m,1H),1.55-1.26(m,7H),1.24-1.13(m,1H),1.00(s,3H),0.87-0.76(m,9H); HRMS(ESI)m / z:calcd forC 15 H 32 NO3S[M+H] + 306.2098 found 306.2096.

[0157] Compound I-40: 1HNMR(400MHz, CDCl3) δ(ppm) 9.94(s, 1H), 7.23 - 7.10(m, 3H), 6.92(ddd, J=7.5, 2.2, 1.5Hz, 1H), 3.38(d, J=15.6Hz, 1H), 3.21(d, J=15.8Hz, 1H), 1.56 - 1.46(m, 3H), 1.46 - 1.39(m, 1H), 1.39 - 1.27(m, 4H), 1.27 - 1.16(m, 1H), 0.96(s, 3H), 0.87 - 0.79(m, 9H); HRMS(ESI) m / z: calcd for C 15 H 32 NO3S[M + H] + 346.1603 found 346.1602。

[0158] Compound I - 43: 1 HNMR(400MHz, CDCl3) δ(ppm) 8.97(s, 2H), 7.35 - 7.19(m, 6H), 7.09(ddd, J=7.9, 2.3, 1.3Hz, 2H), 3.41(d, J=15.6Hz, 2H), 3.23(d, J=15.6Hz, 2H), 1.57 - 1.43(m, 8H), 1.43 - 1.39(m, 4H), 1.39 - 1.31(m, 4H), 1.31 - 1.26(m, 1H), 1.24 - 1.18(m, 2H), 1.05(s, 6H), 0.91 - 0.83(m, 18H); HRMS(ESI) m / z: calcd for C 18 H 29 F3NO2S2[M + H] + 412.1587 found 412.1584。

[0159] Compound I - 45: 1 HNMR(400MHz, CDCl3) δ(ppm) 8.29(s, 1H), 7.24 - 7.19(m, 1H), 6.95 - 6.92m, 2H), 3.37(d, J=15.8Hz, 1H), 3.18(d, J=15.6Hz, 1H), 1.62 - 1.18(m, 9H), 1.03(s, 3H), 0.88 - 0.76(m, 9H); HRMS(ESI) m / z: calcd for C 17 H 28 F2NO2S[M + H] + 348.1804 found 348.1801。

[0160] Example 47: Test of herbicidal activity of compounds

[0161] Seeds of monocotyledonous weeds (barnyard grass) or dicotyledonous weeds (quinoa) were sown in paper cups with a diameter of 7 cm filled with nutrient soil, covered with 1 cm of soil after sowing, suppressed and watered, and cultured in a greenhouse according to conventional methods. When the weeds reached the 2-3 leaf stage, the stems and leaves were sprayed.

[0162] After the original drug was dissolved in acetone, the test solution of the required concentration was prepared with 1% Tween 80 and tap water according to the test requirements. Spray treatment was performed according to the designed test dose (spray pressure 1.95 kg / cm 2 , spray volume 500L / hm 2 ). The test was repeated three times. After treatment, the test materials were placed in the operation hall. After the liquid was dried naturally in the shade, they were placed in the greenhouse and managed according to the conventional method. The reaction of the weeds to the agent was observed and recorded. After treatment, the control effect of the test agent on weeds was visually inspected regularly, and expressed as 0-100%, with "0" representing no control effect and "100%" representing complete kill.

[0163] The test results show that the compounds of formula I generally have excellent control effects on monocotyledonous weeds (barnyard grass) and dicotyledonous weeds (quinoa). Some of the compounds still have good control effects at lower dosages, such as Ⅰ-3, Ⅰ-10, Ⅰ-12, Ⅰ-15, Ⅰ-16, Ⅰ-21, and Ⅰ-22 at an application dosage of 100 g a.i. / hm 2 The control efficiency of barnyard grass was greater than 85%, which was significantly better than the commercial herbicide glyphosate (see Table 2). For example, compounds Ⅰ-26, Ⅰ-32, Ⅰ-33, Ⅰ-40, Ⅰ-43, Ⅰ-44, and Ⅰ-45 had an application dose of 100 g.i. / hm 2 The control efficiency against Chenopodium album was greater than 85%, which was significantly better than the commercially available herbicide glyphosate (see Table 3).

[0164] Table 2

[0165]

Claims

1. A tetrahydrocinnamic acid derivative containing a sulfonamide fragment, characterized in that: The tetrahydrocinnamic acid derivative containing a sulfonamide fragment has a structure shown in Formula I: Where: Selected from n is 0 or 1.

2. A method for preparing the tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 1, characterized in that: Its synthetic route is as follows: The step 1: mixing an oxidizing agent, a chlorinating agent and compound II in a solvent to undergo an oxidative chlorination reaction for 1 to 3 hours; wherein compound II is tetrahydrolinalool or tetrahydrolinaloolmethyl mercaptan; The step 2 is: adding appropriate base and amine compounds to the reaction system of step 1 to cause an amination reaction for 2 to 5 hours, and then post-treating to obtain a tetrahydrocinnamic acid derivative containing a sulfonamide fragment.

3. The method for preparing a tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 2, characterized in that: In step 1, the solvent is selected from any one of acetonitrile, tetrahydrofuran, dioxane, dimethyl sulfoxide, N,N-dimethylformamide, dichloromethane or toluene.

4. The method for preparing a tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 2, characterized in that: In step 1, the oxidant is selected from any one of meta-chloroperbenzoic acid, hydrogen peroxide, sodium hypochlorite, sodium periodate or diacetoxyiodobenzene; and the molar ratio of the oxidant to compound II is (3-5):

1.

5. The method for preparing a tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 2, characterized in that: In step 1, the chlorination reagent is selected from any one of m-dichlorothionyl, oxalyl chloride or N-chlorosuccinimide; the molar ratio of the chlorination reagent to compound II is (1-1.5):

1.

6. The method for preparing a tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 2, characterized in that: The reaction temperature in step 1 is 25-50°C.

7. The method for preparing a tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 2, characterized in that: In step 2, the appropriate base is selected from any one of trimethylamine, triethylamine or pyridine; the amount of the base and compound II is in the following relationship: 1 mmol of compound II corresponds to 0.5-1 ml of the base.

8. The method for preparing the tetrahydrocinnamic acid derivative containing sulfonamide fragment according to claim 2, characterized in that: In step 2, the molar ratio of the amine compound to compound II is (0.8-1):

1.

9. The method for preparing a tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 2, characterized in that: The appropriate temperature in step 2 is 25-50°C.

10. Use of the tetrahydrocinnamic acid derivative containing a sulfonamide fragment according to claim 1 as a herbicide.

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