Nonanoyl vanillylamine derivative as well as preparation method and application thereof

Abstract

The invention relates to a nonanoyl vanillylamine derivative as well as a preparation method and application thereof. The structural general formula of the disclosed nonanoyl vanillylamine derivative is shown as a formula (III), wherein R1 is selected from alkyl, benzyl or substituted benzyl; r2 is selected from alkyl, phenyl or substituted phenyl. Researches show that the nonanoyl vanillylamine derivative has good acaricidal activity on female adult carmine tetranychus cinnabarinus, compared with parent nonanoyl vanillylamine, the contact activity of the nonanoyl vanillylamine derivative is remarkably improved, and the nonanoyl vanillylamine derivative can be used for preparing efficient, low-toxicity and environment-friendly plant source acaricides.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of organic synthesis, and relates to a nonivamide derivative, in particular to a nonivamide derivative, a preparation method and application thereof. BACKGROUND

[0002] Nonivamide is also called synthetic capsaicin and exists naturally in Solanaceae Capsicum plants.

[0003] ; Nonivamide and its derivatives have various biological activities in medicine and pesticides. In medicine, they have anticancer (Free Radical Biology and Medicine, 2018, 120, 147-159), anti-inflammatory (Molecular Nutrition&Food Research, 2017, 61, 1600474), antioxidant (Chemico-Biological Interactions, 2009, 180, 183-192), anti-obesity (Molecular Nutrition&Food Research, 2017, 61, 1600731), analgesic (Journal of Pain Research, 2016, 9, 1221-1230) and antibacterial (Environmental Toxicology and Chemistry, 2013, 32, 802-809) activities. In pesticides, they have insecticidal (Industrial Crops and Products, 2024, 222, 119785) and antibacterial (Frontiers in Chemistry, 2022, 10, 929050) activities. SUMMARY

[0004] Based on the new research findings of the inventors, the purpose of the application is to provide a nonivamide derivative, a preparation method and application thereof.

[0005] To this end, the nonivamide derivative provided by the application has a chemical structural formula as shown in formula (III): ; In the formula, R 1 is selected from alkyl, benzyl or substituted benzyl; R 2 is selected from alkyl, phenyl or substituted phenyl.

[0006] Optionally, in the formula (III), R 1 and R 2 are selected from (1): R1 = methyl; R 2 = -CH=CH2; (2): R 1 = methyl; R 2 = phenyl; (3): R 1 = methyl; R 2 = p-fluorophenyl; (4): R 1 = ethyl; R 2 = -CH=CH2; (5): R 1 = ethyl; R 2 = phenyl; (6): R 1 = ethyl; R 2 = p-fluorophenyl; (7): R 1 = -CH2CH=CH2; R 2 = -CH=CH2; (8): R 1 = -CH2CH=CH2; R 2 = phenyl; (9): R 1 = -CH2CH=CH2; R 2 = p-fluorophenyl; (10): R 1 = -CH2C≡CH; R 2 = -CH=CH2; (11): R 1 = -CH2C≡CH; R 2 = phenyl; (12): R 1 = -CH2C≡CH; R 2 = p-fluorophenyl; (13): R 1 = 3-methyl-2-butenyl; R 2 = -CH=CH2; (14): R 1 = 3-methyl-2-butenyl; R 2 = phenyl; (15): R 1 = 3-methyl-2-butenyl; R 2 = p-fluorophenyl; (16): R 1 = benzyl; R 2 = -CH=CH2; (17): R 1 = benzyl; R 2 = phenyl; (18): R 1 = benzyl; R 2 = p-fluorophenyl; (19): R 1 = p-fluorobenzyl; R 2 = -CH=CH2; (20): R 1 = p-fluorobenzyl; R 2 = phenyl; or (21): R 1 = p-fluorobenzyl; R 2= p-fluorophenyl.

[0007] The present application also provides a preparation method of the above nonoyl vanillamine derivative, which comprises the following steps: Step one, in the presence of inorganic base, nonoyl vanillamine shown in formula (I) is reacted with R 1 X (X = Cl, Br or I) to obtain an intermediate shown in formula (II); ; ; Step two, the intermediate shown in formula (II) is reacted with R 2 COCl to obtain the nonoyl vanillamine derivative.

[0008] Alternatively, the step one reaction is carried out in a first organic solvent, and inorganic base is added, and the reaction temperature is 60-70 o C. The first organic solvent can be acetone. The inorganic base can be potassium carbonate.

[0009] Alternatively, R 1 X in the step one is selected from one of methyl iodide, ethyl iodide, propylene bromide, propargyl bromide, 1-bromo-3-methyl-2-butene, benzyl chloride and p-fluorobenzyl chloride.

[0010] Alternatively, the step two reaction is carried out in a second organic solvent, and organic base is added, and the reaction temperature is 20-30 o C. The second organic solvent can be dichloromethane. The organic base can be triethylamine.

[0011] Alternatively, R 2 COCl in the step two is selected from one of acryloyl chloride, benzoyl chloride and p-fluorobenzoyl chloride.

[0012] The nonoyl vanillamine derivative provided by the present application can be used for preparing acaricides, and some of the compounds have good acaricidal activity against common agricultural pests such as Tetranychus cinnabarinus, and the activity is significantly improved compared with the parent nonoyl vanillamine, and can be used for preparing plant source pesticides with high efficiency, environmental protection and low toxicity. BRIEF DESCRIPTION OF DRAWINGS

[0013] Figure 1 is the nuclear magnetic resonance hydrogen spectrum spectrum of compound 1; Figure 2 is the nuclear magnetic resonance hydrogen spectrum spectrum of compound 2; Figure 3 is the nuclear magnetic resonance hydrogen spectrum spectrum of compound 3; Figure 4 is the nuclear magnetic resonance hydrogen spectrum spectrum of compound 19. DETAILED DESCRIPTION

[0014] The terms used herein are to be interpreted according to their ordinary meaning to a person of ordinary skill in the relevant art, unless explicitly stated otherwise.

[0015] The following gives specific embodiments of the present application, it should be noted that the present application is not limited to the following specific embodiments, any equivalent exchange made on the basis of the technical solutions of the present application falls within the protection scope of the present application. The reaction raw materials and chemical reagents used in the following examples are all commercially available products.

[0016] The synthetic route of the nonanoyl vanillamine derivative described in the present application is as follows: ; First, a suitable amount of nonanoyl vanillamine (I) is dissolved in a suitable organic solvent (such as acetone), and then a suitable amount of potassium carbonate and halogenated hydrocarbon R 1 X is added to the above solution, and an intermediate represented by formula (II) is prepared under suitable conditions (such as 60 o C oil bath). Second, the intermediate represented by formula (II) is reacted with acyl chloride R 2 COCl in a suitable reaction system (such as a reaction system containing triethylamine and dry dichloromethane) and reaction conditions (such as a reaction temperature of 20-30 o C) to prepare the compound of the present application.

[0017] Example 1: Preparation of nonanoyl vanillamine derivative Preparation of the intermediate represented by formula (II): nonanoyl vanillamine (1.0 mmol), potassium iodide (0.2 mmol), and potassium carbonate (2.0 mmol) are dissolved in 6 mL of acetone, and then halogenated hydrocarbon R 1 X (1.5 mmol) is added to the above solution, and then stirred in a 60 o C oil bath for 12 hours; after the reaction is complete, 10 mL of ice water is added, dichloromethane (20 mL x 3) is extracted, the organic phases are combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and then column chromatography is used to separate to obtain the intermediate represented by formula (II). The specific compounds obtained in this example are II-1 to II-7, with a yield of 70-93%. The structures of the compounds corresponding to formula (II) are as follows: II-1: R 1 = methyl (X in R 1 X is I); II-2: R 1 = ethyl (X in R 1 X is I); II-3: R 1 = -CH2CH=CH2 (X in R 1 X is Br); II-4: R 1 = -CH2C≡CH (X in R 1 X is Br); II-5: R1 = 3-methyl-2-butenyl (corresponding R 1 X in X is Cl); II-6: R 1 = benzyl (corresponding R 1 X in X is Cl); II-7: R 1 = p-fluorobenzyl (corresponding R 1 X in X is Cl).

[0018] Preparation of the target compound 1-21: the intermediate shown in formula (II) (1.0 mmol) and triethylamine (2.0 mmol) were dissolved in 5 mL of dry dichloromethane, and acyl chloride R 2 COCl was added to the above solution, and stirred at room temperature for 7 hours; after the reaction was completed, 10 mL of ice water was added, extracted with dichloromethane (20 mL x 3), the organic phases were combined, washed with saturated brine, dried over anhydrous sodium sulfate, concentrated, and separated by thin layer chromatography to obtain the target compound (1-21) with a yield of 23-56%.

[0019] The compound 1-21 prepared by the above preparation method has the following general formula, and corresponds to compounds with structures (1)-(21) respectively: (1): R 1 = methyl (corresponding R 1 X in X is I); R 2 = -CH=CH2; (2): R 1 = methyl (corresponding R 1 X in X is I); R 2 = phenyl; (3): R 1 = methyl (corresponding R 1 X in X is I); R 2 = p-fluorophenyl; (4): R 1 = ethyl (corresponding R 1 X in X is I); R 2 = -CH=CH2; (5): R 1 = ethyl (corresponding R 1 X in X is I); R 2 = phenyl; (6): R 1 = ethyl (corresponding R 1 X in X is I); R 2 = p-fluorophenyl; (7): R 1 = -CH2CH=CH2 (corresponding R 1 X in X is Br); R 2 = -CH=CH2; (8): R 1 = -CH2CH=CH2 (corresponding R 1X in X is Br); R 2 = -CH2CH=CH2(corresponding R 1 X in X is Br); R 1 X in X is Br); R 2 = -CH2C≡CH(corresponding R 1 X in X is Br); R 1 X in X is Br); R 2 = -CH2C≡CH(corresponding R 1 X in X is Br); R 1 X in X is Br); R 2 = -CH2C≡CH(corresponding R 1 X in X is Br); R 1 X in X is Br); R 2 = -CH2C≡CH(corresponding R 1 X in X is Br); R 1 X in X is Br); R 2 = -CH2C≡CH(corresponding R 1 X in X is Br); R 1 X in X is Br); R 2 = -CH2C≡CH(corresponding R 1 X in X is Br); R 1 X in X is Br); R 2 = -CH2C≡CH(corresponding R 1 X in X is Cl); R 1 = -CH2C≡CH(corresponding R 2 X in X is Cl); R 1 = -CH2C≡CH(corresponding R 1 X in X is Cl); R 2 = -CH2C≡CH(corresponding R 1 X in X is Cl); R 1 = -CH2C≡CH(corresponding R 2 X in X is Cl); R 1 = -CH2C≡CH(corresponding R 1 X in X is Cl); R 2 = -CH2C≡CH(corresponding R 1 X in X is Cl); R 1 = -CH2C≡CH(corresponding R 2 X in X is Cl); R 1 = -CH2C≡CH(corresponding R 1 X in X is Cl); R 2= p-fluorophenyl.

[0020] The results of the product identification are as follows: The physicochemical properties of compound 1 are as follows: Colorless liquid; yield: 39% The infrared spectrum and nuclear magnetic resonance hydrogen spectrum data of the compound are as follows: IR cm -1 (KBr): 2928, 2855, 1691, 1515, 1456, 1404, 1253, 1160, 1026; 1 HNMR (400 MHz, CDCl3) δ: 6.81 (d, J = 8.0 Hz, 1H, Ph-H), 6.68-6.75 (m, 3H), 6.44(dd, J = 1.6, 16.8 Hz, 1H, =CH2), 5.79 (dd, J = 1.6, 10.4 Hz, 1H, =CH2), 4.92 (s,2H, -CH2-), 3.86 (s, 3H, -OCH3), 3.85 (s, 3H, -OCH3), 2.72 (t, J = 7.6 Hz, 2H, -CH2-), 1.60-1.68 (m, 2H, -CH2-), 1.24-1.30 (m, 10H), 0.88 (t, J = 6.4 Hz, 3H, -CH3). The physicochemical properties of compound 2 are as follows: Pale yellow oily liquid; yield: 37% The infrared spectrum and nuclear magnetic resonance hydrogen spectrum data of the compound are as follows: IR cm -1 (KBr): 2927, 2855, 1668, 1515, 1453, 1345, 1258, 1146, 1027,713; 1 H NMR (400 MHz, CDCl3) δ: 7.52-7.56 (m, 3H, Ph-H), 7.41-7.45 (m, 2H, Ph-H), 6.79-6.82 (m, 2H, Ph-H), 6.77 (d, J= 8.0 Hz, 1H, Ph-H), 4.93 (s, 2H, -CH2-), 3.84 (s, 3H, -OCH3), 3.82 (s, 3H, -OCH3), 2.33 (t, J = 7.6 Hz, 2H, -CH2-), 1.49-1.56 (m, 2H, -CH2-), 1.10-1.25 (m, 10H), 0.87 (t, J = 7.2 Hz, 3H, -CH3). Physical and chemical properties of compound 3 are as follows: Pale yellow oily liquid; yield: 54% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2855, 1662, 1514, 1457, 1349, 1248, 1150, 1027,807; 1 H NMR (400 MHz, CDCl3) δ: 7.55-7.60 (m, 2H, Ph-H), 7.09-7.13 (m, 2H, Ph-H), 6.81 (d, J = 1.6 Hz, 1H, Ph-H), 6.74-6.79 (m, 2H, Ph-H), 4.92 (s, 2H, -CH2-), 3.84 (s, 3H, -OCH3), 3.83 (s, 3H, -OCH3), 2.34 (t, J = 7.6 Hz, 2H, -CH2-), 1.51-1.58 (m, 2H, -CH2-), 1.13-1.26 (m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). Physical and chemical properties of compound 4 are as follows: Pale yellow oily liquid; yield: 23% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2859, 1691, 1514, 1458, 1401, 1253, 1160, 1038,985; 1 H NMR (400 MHz, CDCl3) δ: 6.81 (d, J= 8.0 Hz, 1H, Ph-H), 6.67-6.75 (m,3H), 6.44 (dd, J = 1.6, 16.8 Hz, 1H, =CH2), 5.78 (dd, J = 1.6, 10.4 Hz, 1H, =CH2),4.91 (s, 2H, -CH2-), 4.09 (q, J = 6.8 Hz, 2H, -CH2-), 3.84 (s, 3H, -OCH3), 2.72(t, J = 7.6 Hz, 2H, -CH2-), 1.60-1.67 (m, 2H, -CH2-), 1.46 (t, J = 6.8 Hz, 3H, -CH3), 1.24-1.30 (m, 10H), 0.88 (t, J = 6.4 Hz, 3H, -CH3). Physical and chemical properties of compound 5 are as follows: Colorless oily liquid; yield: 45% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2858, 1665, 1514, 1455, 1344, 1260, 1141, 1035,712; 1 H NMR (400 MHz, CDCl3) δ: 7.51-7.55 (m, 3H, Ph-H), 7.40-7.44 (m, 2H, Ph-H), 6.81 (d, J = 1.6 Hz, 1H, Ph-H), 6.74-6.79 (m, 2H, Ph-H), 4.93 (s, 2H, -CH2-), 4.08 (q, J = 6.8 Hz, 2H, -CH2-), 3.81 (s, 3H, -OCH3), 2.33 (t, J = 7.6 Hz,2H, -CH2-), 1.49-1.56 (m, 2H, -CH2-), 1.45 (t, J = 7.2 Hz, 3H, -CH3), 1.09-1.27(m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). The physico-chemical properties of compound 6 are as follows: pale yellow oily liquid; yield: 41% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 1643, 1514, 1455, 1353, 1259, 1142, 1034; 1 H NMR (400 MHz, CDCl3) δ: 7.54-7.59 (m, 2H, Ph-H), 7.07-7.13 (m, 2H, Ph-H), 6.80(d, J = 1.6 Hz, 1H, Ph-H), 6.73-6.77 (m, 2H, Ph-H), 4.91 (s, 2H, -CH2-), 4.08(q, J = 6.8 Hz, 2H, -CH2-), 3.81 (s, 3H, -OCH3), 2.34 (t, J = 7.2 Hz, 2H, -CH2-),1.51-1.58 (m, 2H, -CH2-), 1.45 (t, J = 6.8 Hz, 3H, -CH3), 1.15-1.26 (m, 10H),0.87 (t, J = 7.2 Hz, 3H, -CH3). The physico-chemical properties of compound 7 are as follows: pale yellow oily liquid; yield: 41% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2857, 1691, 1513, 1457, 1406, 1258, 1160, 992; 1 HNMR (400 MHz, CDCl3) δ: 6.82 (d, J = 8.0 Hz, 1H, Ph-H), 6.66-6.74 (m, 3H), 6.44(dd, J = 1.6, 16.8 Hz, 1H, =CH2), 6.01-6.11 (m, 1H, -CH=), 5.78 (dd, J= 1.6,10.4 Hz, 1H, =CH2), 5.36-5.41 (m, 1H, =CH2), 5.26-5.29 (m, 1H, =CH2), 4.91 (s,2H, -CH2-), 4.57-4.59 (m, 2H, -CH2-), 3.84 (s, 3H, -OCH3), 2.72 (t, J = 7.6 Hz,2H, -CH2-), 1.60-1.67 (m, 2H, -CH2-), 1.24-1.29 (m, 10H), 0.88 (t, J = 6.4 Hz,3H, -CH3). The physicochemical properties of compound 8 are as follows: Colorless oily liquid; yield: 56% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2857, 1661, 1512, 1454, 1346, 1263, 1141, 1024,712; 1 H NMR (400 MHz, CDCl3) δ: 7.51-7.56 (m, 3H, Ph-H), 7.40-7.44 (m, 2H, Ph-H), 6.76-6.81 (m, 3H, Ph-H), 6.01-6.10 (m, 1H, -CH=), 5.35-5.40 (m, 1H, =CH2), 5.24-5.28 (m, 1H, =CH2), 4.93 (s, 2H, -CH2-), 4.55-4.57 (m, 2H, -CH2-),3.81 (s, 3H, -OCH3), 2.33 (t, J = 7.2 Hz, 2H, -CH2-), 1.49-1.56 (m, 2H, -CH2-),1.11-1.25 (m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). The physicochemical properties of compound 9 are as follows: Colorless oily liquid; yield: 47% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1IR cm"1(KBr): 2928, 2858, 1645, 1512, 1455, 1354, 1259, 1147, 1025; 1 HNMR (400 MHz, CDCl3) δ: 7.54-7.59 (m, 2H, Ph-H), 7.08-7.13 (m, 2H, Ph-H),6.81 (d, J = 2.0 Hz, 1H, Ph-H), 6.78 (d, J = 8.0 Hz, 1H, Ph-H), 6.74 (dd, J = 2.0,8.4 Hz, 1H, Ph-H), 6.01-6.10 (m, 1H, -CH=), 5.35-5.40 (m, 1H, =CH2), 5.25-5.28 (m, 1H, =CH2), 4.91 (s, 2H, -CH2-), 4.56-4.58 (m, 2H, -CH2-), 3.82 (s,3H, -OCH3), 2.35 (t, J = 7.2 Hz, 2H, -CH2-), 1.51-1.58 (m, 2H, -CH2-), 1.15-1.26(m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). The physicochemical properties of compound 10 are as follows: Colorless oily liquid; yield: 30% The infrared spectrum and proton nuclear magnetic resonance spectrum data of the compound are as follows: IR cm -1 IR cm"1(KBr): 2928, 2859, 1639, 1514, 1456, 1404, 1256, 1163, 993; 1 HNMR (400 MHz, CDCl3) δ: 6.98 (d, J = 8.0 Hz, 1H, Ph-H), 6.67-6.75 (m, 3H), 6.44(dd, J = 1.6, 16.8 Hz, 1H, -CH=), 5.79 (dd, J = 1.6, 10.4 Hz, 1H, -CH=), 4.92 (s,2H, -CH2-), 4.74 (d, J= 2.4 Hz, 2H, -CH2-), 3.84 (s, 3H, -OCH3), 2.73 (t, J = 7.6Hz, 2H, -CH2-), 2.50 (t, J = 2.4 Hz, 1H, ≡CH), 1.61-1.68 (m, 2H, -CH2-), 1.24-1.30 (m, 10H), 0.88 (t, J = 6.4 Hz, 3H, -CH3). Physical and chemical properties of compound 11 are as follows: Light yellow oily liquid; yield: 51% The infrared spectrum and nuclear magnetic resonance hydrogen spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2857, 1654, 1512, 1453, 1347, 1266, 1142, 1023, 969; 1 H NMR (400 MHz, CDCl3) δ: 7.52-7.56 (m, 3H, Ph-H), 7.41-7.45 (m, 2H, Ph-H), 6.93 (d, J = 8.0 Hz, 1H, Ph-H), 6.84 (d, J = 2.0 Hz, 1H, Ph-H), 6.81 (dd, J =2.0, 8.0 Hz, 1H, Ph-H), 4.94 (s, 2H, -CH2-), 4.72 (d, J = 2.4 Hz, 2H, -CH2-),3.82 (s, 3H, -OCH3), 2.49 (t, J = 2.0 Hz, 1H, ≡CH), 2.33 (t, J = 7.6 Hz, 2H, -CH2-), 1.49-1.57 (m, 2H, -CH2-), 1.10-1.27 (m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). Physical and chemical properties of compound 12 are as follows: Light yellow oily liquid; yield: 48% The infrared spectrum and nuclear magnetic resonance hydrogen spectrum data of this compound are as follows: IR cm -1IR cm"1(KBr): 2928, 2858, 1660, 1511, 1456, 1348, 1264, 1145, 1023, 969; 1 H NMR (400 MHz, CDCl3) δ: 7.56-7.59 (m, 2H, Ph-H), 7.08-7.14 (m, 2H, Ph-H), 6.94 (d, J = 8.0 Hz, 1H, Ph-H), 6.83 (d, J = 2.0 Hz, 1H, Ph-H), 6.78 (dd, J =2.0, 8.4 Hz, 1H, Ph-H), 4.92 (s, 2H, -CH2-), 4.73 (d, J = 2.4 Hz, 2H, -CH2-),3.82 (s, 3H, -OCH3), 2.49 (t, J = 2.0 Hz, 2H, ≡CH), 2.35 (t, J = 7.6 Hz, 2H, -CH2-), 1.51-1.58 (m, 2H, -CH2-), 1.15-1.26 (m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). The physicochemical properties of compound 13 are as follows: Light yellow oily liquid; yield: 39% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2925, 2858, 1691, 1514, 1455, 1402, 1244, 1163, 986,789; 1 H NMR (400 MHz, CDCl3) δ: 6.81 (d, J = 8.0 Hz, 1H, Ph-H), 6.66-6.75 (m,3H), 6.44 (dd, J = 1.6, 16.8 Hz, 1H, =CH2), 5.78 (dd, J = 1.6, 10.4 Hz, 1H, =CH2),5.47-5.52 (m, 1H, -CH=), 4.91 (s, 2H, -CH2-), 4.56 (d, J= 6.4 Hz, 2H, -CH2-),3.83 (s, 3H, -OCH3), 2.72 (t, J = 7.2 Hz, 2H, -CH2-), 1.76 (s, 3H, -CH3), 1.71(s, 3H, -CH3), 1.60-1.68 (m, 2H, -CH2-), 1.24-1.32 (m, 10H), 0.88 (t, J = 6.4Hz, 3H, -CH3). Physical and chemical properties of compound 14 are as follows: Light yellow oily liquid; yield: 52% The infrared spectrum and nuclear magnetic resonance hydrogen spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2858, 1663, 1512, 1453, 1344, 1261, 1140, 975; 1 HNMR (400 MHz, CDCl3) δ: 7.51-7.56 (m, 3H, Ph-H), 7.40-7.45 (m, 2H, Ph-H),6.75-6.80 (m, 3H, Ph-H), 5.46-5.51 (m, 1H, -CH=), 4.93 (s, 2H, -CH2-), 4.54(d, J = 6.8 Hz, 2H, -CH2-), 3.80 (s, 3H, -OCH3), 2.33 (t, J = 7.6 Hz, 2H, -CH2-),1.75 (s, 3H, -CH3), 1.71 (s, 3H, -CH3), 1.49-1.55 (m, 2H, -CH2-), 1.11-1.27(m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). Physical and chemical properties of compound 15 are as follows: Light yellow oily liquid; yield: 36% The infrared spectrum and nuclear magnetic resonance hydrogen spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2859, 1669, 1513, 1456, 1346, 1258, 1143, 976; 1HNMR (400 MHz, CDCl3) δ: 7.54-7.59 (m, 2H, Ph-H), 7.08-7.13 (m, 2H, Ph-H),6.79 (d, J = 2.0 Hz, 1H, Ph-H), 6.78 (d, J = 8.4 Hz, 1H, Ph-H), 6.75 (dd, J = 1.6,8.0 Hz, 1H, Ph-H), 5.46-5.51 (m, 1H, -CH=), 4.91 (s, 2H, -CH2-), 4.54 (d, J =6.8 Hz, 2H, -CH2-), 3.80 (s, 3H, -OCH3), 2.35 (t, J = 7.6 Hz, 2H, -CH2-), 1.75(s, 3H, -CH3), 1.71 (s, 3H, -CH3), 1.51-1.57 (m, 2H, -CH2-), 1.15-1.28 (m,10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). The physicochemical properties of compound 16 are as follows: Light yellow oily liquid; yield: 33% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2859, 1666, 1511, 1455, 1346, 1237, 1145, 976,767; 1 H NMR (400 MHz, CDCl3) δ: 7.40-7.43 (m, 2H, Ph-H), 7.33-7.37 (m, 2H, Ph-H), 7.26-7.31 (m, 1H, Ph-H), 6.82 (d, J = 8.0 Hz, 1H, Ph-H), 6.74 (d, J = 2.4 Hz,1H, Ph-H), 6.73 (dd, J = 10.4, 16.8 Hz, 1H, -CH=), 6.64 (dd, J = 2.0, 8.0 Hz, 1H,Ph-H), 6.43 (dd, J= 1.6, 16.8 Hz, 1H, =CH2), 5.78 (dd, J = 1.6, 10.0 Hz, 1H, =CH2), 5.12 (s, 2H, -CH2-), 4.90 (s, 2H, -CH2-), 3.85 (s, 3H, -OCH3), 2.71 (t, J = 7.6 Hz, 2H, -CH2-), 1.59-1.67 (m, 2H, -CH2-), 1.24-1.29 (m, 10H), 0.88 (t, J =6.8 Hz, 3H, -CH3). The physical and chemical properties of compound 17 are as follows: Light yellow oily liquid; yield: 32% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2929, 2859, 1642, 1514, 1455, 1358, 1261, 1141, 1029,767; 1 H NMR (400 MHz, CDCl3) δ: 7.51-7.55 (m, 3H, Ph-H), 7.39-7.43 (m, 4H, Ph-H), 7.33-7.37 (m, 2H, Ph-H), 7.26-7.30 (m, 1H, Ph-H), 6.83 (d, J = 2.0 Hz, 1H,Ph-H), 6.78 (d, J = 8.4 Hz, 1H, Ph-H), 6.72 (dd, J = 2.0, 8.4 Hz, 1H, Ph-H), 5.11(s, 2H, -CH2-), 4.92 (s, 2H, -CH2-), 3.83 (s, 3H, -OCH3), 2.33 (t, J = 7.6 Hz,2H, -CH2-), 1.49-1.56 (m, 2H, -CH2-), 1.11-1.25 (m, 10H), 0.87 (t, J = 6.8 Hz,3H, -CH3). The physical and chemical properties of compound 18 are as follows: Light yellow oily liquid; yield: 47% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2928, 2858, 1644, 1513, 1456, 1356, 1260, 1143, 1026,768; 1 H NMR (400 MHz, CDCl3) δ: 7.54-7.57 (m, 2H, Ph-H), 7.40-7.42 (m, 2H, Ph-H), 7.33-7.37 (m, 2H, Ph-H), 7.26-7.30 (m, 1H, Ph-H), 7.07-7.11 (m, 2H, Ph-H), 6.82 (d, J = 1.6 Hz, 1H, Ph-H), 6.78 (d, J = 8.4 Hz, 1H, Ph-H), 6.70 (dd, J =2.0, 8.4 Hz, 1H, Ph-H), 5.11 (s, 2H, -CH2-), 4.90 (s, 2H, -CH2-), 3.83 (s, 3H,-OCH3), 2.34 (t, J = 7.2 Hz, 2H, -CH2-), 1.50-1.57 (m, 2H, -CH2-), 1.13-1.26 (m,10H), 0.87 (t, J = 7.2 Hz, 3H, -CH3). The physical and chemical properties of compound 19 are as follows: Light yellow oily liquid; yield: 34% The infrared spectrum and proton nuclear magnetic resonance spectrum data of this compound are as follows: IR cm -1 (KBr): 2926, 2857, 1650, 1513, 1458, 1352, 1226, 1149, 1024,804; 1 H NMR (400 MHz, CDCl3) δ: 7.36-7.41 (m, 2H, Ph-H), 7.01-7.07 (m, 2H, Ph-H), 6.81 (d, J = 8.4 Hz, 1H, Ph-H), 6.74 (d, J = 2.0 Hz, 1H, Ph-H), 6.73 (dd, J =10.0, 16.4 Hz, 1H, -CH=), 6.66 (dd, J= 2.4, 8.4 Hz, 1H, Ph-H), 6.44 (dd, J =1.6, 16.8 Hz, 1H, =CH2), 5.78 (dd, J = 1.6, 10.4 Hz, 1H, =CH2), 5.06 (s, 2H, -CH2-), 4.90 (s, 2H, -CH2-), 3.84 (s, 3H, -OCH3), 2.71 (t, J = 7.6 Hz, 2H, -CH2-), 1.62-1.67 (m, 2H, -CH2-), 1.24-1.30 (m, 10H), 0.88 (t, J = 6.4 Hz, 3H, -CH3). The physical and chemical properties of compound 20 are as follows: Light yellow oily liquid; yield: 38% The infrared spectrum and nuclear magnetic resonance hydrogen spectrum data of this compound are as follows: IR cm -1 (KBr): 2927, 2858, 1688, 1513, 1455, 1261, 1148, 1024, 802; 1 HNMR (400 MHz, CDCl3) δ: 7.52-7.56 (m, 3H, Ph-H), 7.35-7.44 (m, 4H, Ph-H),7.00-7.06 (m, 2H, Ph-H), 6.83 (d, J = 2.0 Hz, 1H, Ph-H), 6.77 (d, J = 8.4 Hz, 1H,Ph-H), 6.74 (dd, J = 1.6, 8.0 Hz, 1H, Ph-H), 5.05 (s, 2H, -CH2-), 4.92 (s, 2H,-CH2-), 3.82 (s, 3H, -OCH3), 2.32 (t, J = 7.2 Hz, 2H, -CH2-), 1.49-1.54 (m, 2H,-CH2-), 1.10-1.25 (m, 10H), 0.87 (t, J = 6.8 Hz, 3H, -CH3). The physical and chemical properties of compound 21 are as follows: Light yellow oily liquid; yield: 53% The infrared spectrum and proton nuclear magnetic resonance spectrum data of the compound are as follows: IR cm -1 (KBr): 2927, 2858, 1664, 1512, 1458, 1262, 1227, 1147, 1025,818; 1 H NMR (400 MHz, CDCl3) δ: 7.54-7.59 (m, 2H, Ph-H), 7.36-7.40 (m, 2H, Ph-H), 7.08-7.12 (m, 2H, Ph-H), 7.01-7.06 (m, 2H, Ph-H), 6.82 (d, J = 2.0 Hz, 1H,Ph-H), 6.77 (d, J = 8.0 Hz, 1H, Ph-H), 6.72 (dd, J = 2.0, 8.4 Hz, 1H, Ph-H), 5.05(s, 2H, -CH2-), 4.90 (s, 2H, -CH2-), 3.82 (s, 3H, -OCH3), 2.34 (t, J = 7.6 Hz,2H, -CH2-), 1.52-1.56 (m, 2H, -CH2-), 1.14-1.26 (m, 10H), 0.87 (t, J = 6.8 Hz,3H, -CH3). Example 2: Bioassay experiment of the test compound on Tetranychus cinnabarinus i. Test insects: Tetranychus cinnabarinus Biosduval female adult mites are the sensitive strain of the Plant Protection Laboratory of Northwest A&F University.

[0021] ii. Samples and reagents: Spirodiclofen (98.32%, purchased from Shaanxi Meibang Pesticide Co., Ltd.) (positive control drug), parent Spirodiclofen, intermediates (II-1~II-7) prepared in Example 1, and target compound 1-21, acetone, distilled water, and Tween 80.

[0022] iii. Bioassay method: slide immersion method: ① 0.1‰ Tween 80 stock solution preparation: 25 mg of Tween 80 was dissolved in 5 mL of acetone solution, and distilled water was used to dissolve to 250 mL for use. ② Preparation of test drug solution: 2-3 mg of each test compound was dissolved in 2% acetone (2% of the target volume), and then diluted with 0.1‰ Tween 80 solution to 0.5 mg / mL.

[0023] ③ Preparation of test mites: a 1 cm wide double-sided tape was attached to one end of a glass slide, and healthy and active female T. cinnabarinus mites of the same age were selected with a No. 0 brush and carefully attached to the back of the double-sided tape, about 35 mites per glass slide, in two rows. The glass slide with the test mites was placed in an iron dish lined with a wet sponge and placed in a light incubator at 26±1℃, 60%-80% relative humidity, and light L:D = 14h:10h. After 4 hours, the number of live mites on each glass slide was recorded under a stereomicroscope, and dead and inactive individuals were removed. ④ Drug immersion: the end of the glass slide with the mites was immersed in the test drug solution for 5 seconds, and then excess drug solution was carefully absorbed with a small filter paper strip (without touching the mite body), and then placed back in the iron dish in the same incubation conditions. One glass slide was one treatment, and each treatment was repeated three times. The 0.1‰ Tween 80 solution was used as a blank control. ⑤ Result statistics: the glass slide was removed after 24 hours of drug immersion treatment and the results were examined under a stereomicroscope. The mite body was gently touched with a brush tip, and those with immobile chelicerae were considered dead. The number of dead individuals was recorded, and the observation was recorded for 72 hours. The mortality rate (%) and corrected mortality rate (%) of the test insects were calculated according to the following formula.

[0024] ;

[0025] Table 1. Acaricidal activity of nonanoyl vanillamines, intermediates (II-1~II-7) and derivatives (1-21) of the present application against female T. cinnabarinus mites at a concentration of 0.5 mg / mL.

[0026]

[0027] Conclusion: The results show that the 72h acaricidal activity of most of the above nonanoyl vanillamine derivatives is improved compared to the parent nonanoyl vanillamine, especially compounds 1, 3, 9, 12, 13 and 15, which have significantly improved 72h acaricidal activity. Therefore, they are expected to be used for the preparation of high-efficiency, environmentally friendly and low-toxicity botanical acaricides. Obviously, the above embodiments of the present application are merely exemplary but not intended to limit the embodiments of the present application. Based on the above description, any other variations or changes can be made by those skilled in the art without departing from the spirit and principles of the present application. It is not necessary to list all the embodiments here. Any modifications, equivalent replacements, and improvements made within the spirit and principles of the present application shall fall within the scope of the claims of the present application.

Claims

1. A nonanoyl vanillinamine derivative, characterized in that, Its chemical structural formula is shown in formula (III): ； In the formula: R 1 Selected from alkyl, benzyl, or substituted benzyl groups; R 2 Selected from alkyl, phenyl, or substituted phenyl.

2. The nonanoyl vanillinamine derivative as described in claim 1, characterized in that, The R mentioned 1 and R 2 Selected from: (1) R 1 = Methyl; R 2 = -CH=CH2; (2) R 1 = Methyl; R 2 =Phenyl; (3) R 1 = Methyl; R 2 = p-Fluorophenyl; (4) R 1 = Ethyl; R 2 = -CH=CH2; (5) R 1 = Ethyl; R 2 =Phenyl; (6) R 1 = Ethyl; R 2 = p-Fluorophenyl; (7)R 1 = -CH2CH=CH2;R 2 = -CH=CH2; (8) R 1 = -CH2CH=CH2;R 2 =Phenyl; (9) R 1 = -CH2CH=CH2;R 2 = p-Fluorophenyl; (10)R 1 = -CH2C≡CH;R 2 = -CH=CH2; (11) R 1 = -CH2C≡CH;R 2 =Phenyl; (12) R 1 = -CH2C≡CH;R 2 = p-Fluorophenyl; (13) R 1 = 3-Methyl-2-butenyl; R 2 = -CH=CH2; (14) R 1 = 3-Methyl-2-butenyl; R 2 =Phenyl; (15) R 1 = 3-Methyl-2-butenyl; R 2 = p-Fluorophenyl; (16) R 1 = benzyl; R 2 = -CH=CH2; (17) R 1 = benzyl; R 2 =Phenyl; (18) R 1 = benzyl; R 2 = p-Fluorophenyl; (19) R 1 = p-Fluorobenzyl; R 2 = -CH=CH2; (20)R 1 = p-Fluorobenzyl; R 2 = phenyl; or (21) R 1 = p-Fluorobenzyl; R 2 = p-Fluorophenyl.

3. The method for preparing nonanoyl vanillinamine derivatives as described in claim 1, characterized in that, Includes the following steps: Step 1, nonanoyl vanillinylamine and haloalkanes R 1 The intermediate shown in formula (II) is prepared by reaction X; ； Step 2, the intermediate shown in formula (II) reacts with acyl chloride R 2 Nonanoyl vanillinamine derivatives were prepared by COCl reaction.

4. The method for preparing nonanoyl vanillinamine derivatives as described in claim 3, characterized in that, Step one reaction is carried out in the first organic solvent, with the addition of an inorganic base, at a reaction temperature of 60-70°C. o C.

5. The method for preparing nonanoyl vanillinamine derivatives as described in claim 3, characterized in that, Step two of the reaction is carried out in a second organic solvent, with the addition of an organic base, at a reaction temperature of 20-30°C. o C.

6. The method for preparing nonanoyl vanillinamine derivatives as described in claim 3, characterized in that, The haloalkane R in step one 1 X is selected from iodomethane, iodoethane, bromopropene, bromopropyne, 1-bromo-3-methyl-2-butene, benzyl chloride, or p-fluorobenzyl chloride.

7. The method for preparing nonanoyl vanillinamine derivatives as described in claim 3, characterized in that, In step two, acyl chloride R 2 COCl is selected from acryloyl chloride, benzoyl chloride, or p-fluorobenzoyl chloride.

8. The use of the nonanoyl vanillinamine derivatives as described in claim 1 or 2 in the preparation of acaricides.

9. The use of the nonanoyl vanillinamine derivatives as described in claim 1 or 2 in the preparation of a cinnabar spider mite icide.

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