N,N'-bis-monoterpenoid imidazole quaternary ammonium salt and its synthesis method and application

Abstract

The invention discloses an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt and a synthesis method and application thereof, and belongs to the field of antibacterial materials. The synthesis method of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt comprises the following steps: adding N-monoterpenoid imidazole and a halogenated product containing a monoterpenoid group to an organic solvent for quaternization reaction, and then performing purification treatment to obtain the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt; the N-monoterpenoid imidazole is N-hydrogenated imidazole or N-tetrahydrogeranyl imidazole; and the halogenated product containing a monoterpenoid group is any one of hydrogenated imidazole bromide, hydrogenated imidazole chloride, tetrahydrogeranyl bromide, tetrahydrogeranyl chloride and isobornyl methyl bromide. The N,N'-bis-monoterpenoid imidazole quaternary ammonium salt synthesized by the present invention can be used to inhibit plant pathogens such as rice sheath blight, pine blight, tea fruit spiny colleorhiza, watermelon wilt, tobacco black shank pathogen, loquat anthracnose pathogen, Coriolus versicolor, and Fusarium verticillium.

Description

Technical Field

[0001] The invention relates to the field of antibacterial materials, in particular to an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt and a synthesis method and application thereof. Background Art

[0002] In order to explore and expand the deep processing application of rosin turpentine and litsea cubeba oil, Jiangxi Agricultural University has studied and synthesized a series of hydrogenated nopyl derivatives, camphene derivatives, and hydrogenated citronellal derivatives, and conducted application tests in insect repellent and antibacterial. The study showed that quaternary ammonium salts containing hydrogenated nopyl have a good inhibitory effect on the growth of some plant pathogenic fungi, among which the monoquaternary ammonium salt of dihydrogenated nopyl has a stronger antibacterial effect and has a significant inhibitory effect on a variety of plant pathogenic fungi.

[0003] However, the above compounds are all synthesized using β-pinene, one of the main components of turpentine oil, as the initial raw material, and quaternary ammonium salts are not synthesized using Litsea cubeba oil as the initial raw material; therefore, in order to further expand the deep processing application of Litsea cubeba oil and explore more compounds that have obvious inhibitory effects on a variety of plant pathogenic fungi, it is necessary to conduct a deeper study on the application of Litsea cubeba oil. Summary of the invention

[0004] The object of the present invention is to provide a method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salts to solve the problems raised in the above background technology.

[0005] To achieve the above objectives, the embodiments of the present invention provide the following technical solutions:

[0006] A method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salts, comprising the following steps:

[0007] N-monoterpene imidazole and a halide containing a monoterpene group are added to an organic solvent for quaternization reaction, and then purified to obtain the N,N'-bis-monoterpene imidazole quaternary ammonium salt; the N-monoterpene imidazole is N-hydrogenated imidazole or N-tetrahydrogeranyl imidazole; the halide containing a monoterpene group is any one of hydrogenated imidazole bromide, hydrogenated imidazole chloride, tetrahydrogeranyl bromide, tetrahydrogeranyl chloride and isobornyl methyl bromide.

[0008] Preferably, the organic solvent is at least one of ethanol, ethyl acetate, cyclohexane and acetonitrile.

[0009] Preferably, the quaternization reaction method is a heating reflux reaction or a hydrothermal synthesis reaction.

[0010] Preferably, the molar ratio of the N-monoterpene imidazole to the halide containing a monoterpene group is 1:(1-1.1).

[0011] Preferably, the purification method comprises the following steps: after the reaction is completed, the organic solvent is evaporated, the residue is washed with petroleum ether, and after the organic solvent is removed, vacuum decompression treatment is performed to obtain the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt.

[0012] Another object of the present invention is to provide an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt prepared by the above synthesis method.

[0013] Preferably, the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt is any one of N,N'-dihydrogenated imidazole bromide, N,N'-dihydrogenated imidazole chloride, N,N'-di-tetrahydrogeranyl imidazole bromide, N,N'-di-tetrahydrogeranyl imidazole chloride, N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole bromide, N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole chloride, N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole bromide, N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole chloride, N-hydrogenated imidazole-N'-isobornylmethyl imidazole bromide, and N-tetrahydrogeranyl-N'-isobornylmethyl imidazole bromide.

[0014] Another object of the present invention is to provide an application of the above-mentioned N,N'-bis-monoterpenoid imidazole quaternary ammonium salt in antibacterial applications.

[0015] Preferably, the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt is used to inhibit plant pathogens.

[0016] Preferably, the plant pathogens include at least rice sheath blight, pine tip blight, tea fruit thorn spore pathogen, watermelon wilt pathogen, tobacco black shank pathogen, loquat anthracnose pathogen, Coriolus versicolor, and Fusarium solani.

[0017] The invention provides a method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salts. The method uses N-monoterpenoid imidazole and a halogenated product containing a monoterpenoid group as raw materials. The synthesized N,N'-bis-monoterpenoid imidazole quaternary ammonium salts can be used to inhibit plant pathogens such as rice sheath blight pathogen, pine blight pathogen, tea fruit spiny colleorhiza, watermelon wilt pathogen, tobacco black shank pathogen, loquat anthrax pathogen, coriolus versicolor, and Fusarium verticillaster. In addition, the synthesis method provided by the invention requires simple instruments and equipment, is easy to operate, has mild and easily controllable conditions, and has high product yield and purity. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 2;

[0019] Figure 2 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 2;

[0020] Figure 3The carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 2;

[0021] Figure 4 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 3;

[0022] Figure 5 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 3;

[0023] Figure 6 The carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 3;

[0024] Figure 7 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 4;

[0025] Figure 8 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 4;

[0026] Fig. 9 The carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 4;

[0027] Fig.10 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 5;

[0028] Fig.11 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 5;

[0029] Fig.12 The carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 5;

[0030] Fig.13 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 6;

[0031] Fig.14 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 6;

[0032] Fig.15 The carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 6;

[0033] Fig.16 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 7;

[0034] Fig.17 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 7;

[0035] Fig.18 The carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 7;

[0036] Fig.19 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 8;

[0037] Fig. 20 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 8;

[0038] Fig.21 The carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 8;

[0039] Fig. 22 The infrared spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 9;

[0040] Fig.23 The hydrogen spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 9;

[0041] Fig.24 This is the carbon spectrum of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt provided in Example 9. DETAILED DESCRIPTION

[0042] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] In one embodiment of the present invention, a method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salt is provided, which comprises the following steps:

[0044] N-monoterpene imidazole and a halide containing a monoterpene group are added to an organic solvent for quaternization reaction, and then purified to obtain the N,N'-bis-monoterpene imidazole quaternary ammonium salt; the N-monoterpene imidazole is N-hydrogenated imidazole (RM) or N-tetrahydrogeranyl imidazole (R'M); the halide containing a monoterpene group is any one of hydrogenated imidazole bromide (RBr), hydrogenated imidazole chloride (RCl), tetrahydrogeranyl bromide (R'Br), tetrahydrogeranyl chloride (R'Cl), and isobornyl methyl bromide (HK-Br).

[0045] The raw material of hydrogenated nopyl is a β-pinene derivative, and the raw material of tetrahydrogeranyl is a derivative of citral, the main component of litsea cubeba oil.

[0046] In addition, the structural formula of N-hydrogenated imidazole (RM) is:

[0047] ;

[0048] The structural formula of N-tetrahydrogeranyl imidazole (R'M) is:

[0049] ;

[0050] The structural formula of hydronopyl bromide (RBr) is:

[0051] ;

[0052] The structural formula of hydronopyl chloride (RCl) is:

[0053] ;

[0054] The structural formula of tetrahydrogeranyl bromide (R'Br) is:

[0055] ;

[0056] The structural formula of tetrahydrogeranyl chloride (R'Cl) is:

[0057] ;

[0058] The structural formula of isobornylmethyl bromide (HK-Br) is:

[0059] .

[0060] The chemical reaction route of the above-mentioned synthesis method is as follows:

[0061] ;

[0062] ;

[0063] ;

[0064] Specifically, the above synthesis method may include at least the following 8 chemical reaction equations:

[0065] RM + RBr → RMR-Br (1)

[0066] RM + RCl → RMR-Cl (2)

[0067] R'M + R'Br→R'-M-R'-Br (3)

[0068] R'M + R'Cl→R'-M-R'-Cl (4)

[0069] RM + R'Br→RM-R'-Br ←RBr + R'M (5)

[0070] RM + R'Cl→RM-R'-Cl ←RCl + R'M (6)

[0071] RM + HK-Br → RM-HK-Br (7)

[0072] R'M + HK-Br→R'-M-HK-Br (8).

[0073] In a preferred embodiment of the present invention, the organic solvent is at least one of ethanol, ethyl acetate, cyclohexane and acetonitrile.

[0074] In a preferred embodiment of the present invention, the quaternization reaction method is a heating reflux reaction or a hydrothermal synthesis reaction.

[0075] In a preferred embodiment of the present invention, the molar ratio of N-monoterpene imidazole to the halide containing a monoterpene group is 1:(1-1.1).

[0076] In a preferred embodiment of the present invention, the purification method comprises the following steps: after the reaction is completed, the organic solvent is evaporated, the residue is washed with petroleum ether, and after the organic solvent is removed, vacuum decompression treatment is performed to obtain the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt.

[0077] In a preferred embodiment of the present invention, the following 8 N,N'-bis-monoterpenoid imidazole quaternary ammonium salts can be synthesized by the above-mentioned synthesis method: N,N'-dihydrogenated imidazole bromide (RMR-Br), N,N'-dihydrogenated imidazole chloride (RMR-Cl), N,N'-di-tetrahydrogeranyl imidazole bromide (R'-M-R'-Br), N,N'-di-tetrahydrogeranyl imidazole chloride (R'-M-R'-Cl), N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole bromide (RM-R'-Br), N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole chloride (RM-R'-Cl), N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole bromide (RM-R'-Br), N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole chloride (RM-R'-Cl), N-hydrogenated imidazole-N'-isobornyl methyl bromide (RM-HK-Br), and N-tetrahydrogeranyl-N'-isobornyl methyl imidazole bromide (R'-M-HK-Br). There are no related reports on these eight compounds at home or abroad.

[0078] In another embodiment of the present invention, there is provided an application of the above-mentioned N,N'-bis-monoterpenoid imidazole quaternary ammonium salt in antibacterial applications.

[0079] Specifically, the above-mentioned N,N'-bis-monoterpenoid imidazole quaternary ammonium salt is used to inhibit plant pathogens; wherein the plant pathogens at least include rice sheath blight (K), pine blight (S), tea fruit spiny spore fungus (Cf), watermelon wilt (X), tobacco black shank fungus (11), loquat anthracnose (P), coriolus versicolor (V), and Fusarium solani (O).

[0080] The antibacterial activity characteristics of the above-mentioned N,N'-bis-monoterpenoid imidazole quaternary ammonium salts are: the mycelium growth rate method is adopted, with chlorothalonil as the positive control, and 8 plant pathogenic fungi such as rice sheath blight, pine blight, tea fruit spiny Colletotrichum, watermelon wilt, tobacco black shank, loquat anthracnose, Coriolus verticillaster and Fusarium solani are used as test fungi to determine the antibacterial activity of 8 quaternary ammonium salt compounds; the test results show that the 8 compounds have relatively high inhibition rates against rice sheath blight, pine blight, watermelon wilt and tobacco black shank.

[0081] In addition, the synthetic method provided in the embodiment of the present invention requires simple instruments and equipment (agitator, rotary evaporator, vacuum pump, etc.), is easy to operate, has mild and easy-to-control conditions, and has high product yield and purity.

[0082] The following embodiments are some specific implementation cases and application cases of the present invention in practical applications, but are not limited thereto.

[0083] Example 1: This example provides a general method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salts, which specifically includes the following steps:

[0084] 0.012mol of N-hydrogenated imidazole (RM) or N-tetrahydrogeranyl imidazole (R'M), 0.014mol of hydrogenated imidazole bromide (RBr) or other monoterpene halides U (RCl, R'Br, R'Cl, HK-Br), 50mL of anhydrous ethanol, are placed in a 100mL ground-mouth conical flask with a magnetic stirrer, then mounted on a magnetic stirrer, and a reflux condenser is inserted, stirred and heated to about 80°C, and allowed to react under reflux for several hours. Samples can be taken during the reaction for gas chromatography analysis. When it is found that there is no more raw material RM or R'M, the heating and stirring are terminated, the reaction solution is transferred to a round-bottom flask, concentrated and the organic solvent is removed by rotary evaporation, and the residue in the flask is washed with petroleum ether for 3-5 times. After removing the petroleum ether, vacuum decompression treatment is performed to obtain the desired N,N'-bis-monoterpene imidazole type quaternary ammonium salt product.

[0085] Example 2: This example provides an N, N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, RM and RBr are reacted, and the other aspects are the same as in Example 1 to obtain N, N'-dihydro-no-imidazolium bromide (RMR-Br), a white solid, mp.70.6~71.4℃, and a yield of 86%. Its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 1-Figure 3 As shown; 1 H NMR (400MHz, CDCl3), δ (ppm) : 10.415(s, 1H, α- H), 7.567(s, 2H, β- CH, γ- CH), 4.335(m,4H, 2 11- CH2), 2.339(m, 2H, 2 2- CH), 2.062~1.847[m, 16H, 2 ( 10- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2)], 1.530(m, 2H, 2 3- CH), 1.184(s, 6H, 2 9- CH3), 1.016(s, 6H, 2 8- CH3), 0.871(d, J=9.6Hz, 2H, 2 7- CH); 13 C NMR (100MHz, CDCl3), δ (ppm) : 136.89(C -α ), 122.23(C -β , C -γ ), 48.77(2 C -11 ), 46.03(2 C -2 ), 41.12(2 C -5 ), 38.59(2 C -6 ),38.04(2 C -1 ), 37.95(2 C -10 ), 33.36(2 C -7 ), 27.95(2 C -9 ), 26.10(2 C -4 ), 23.26(2C -8 ), 21.77(2 C -3 ); IR (KBr), νmax (cm -1 ): 3452, 3129, 3049, 2982, 2935, 2860,1760, 1729, 1646, 1562, 1468, 1383, 1364, 1278, 1227, 1117, 1088, 978, 955,865, 751.

[0086] Example 3: This example provides an N, N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, RM and RCl are reacted, and the other aspects are the same as in Example 1 to obtain N, N'-dihydro-no-imidazolium chloride (RMR-Cl), a white solid, mp. 69.9-70.8 ° C, and a yield of 83%; its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 4-Figure 6 As shown; 1 H NMR (400MHz, CDCl3), δ (ppm) : 10.449(s, 1H, α- CH), 7.507(s, 2H, β- CH, γ- CH), 4.350 (m,4H, 2 11- CH2), 2.331(m, 2H, 2 2- CH), 2.002~1.850[m, 16H, 2 ( 10- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2)], 1.519(m, 2H, 2 3- CH), 1.181(s, 6H, 2 9- CH3), 1.011(s, 6H, 2 8- CH3), 0.866(d, J=9.6Hz, 2H, 2 7- CH); 13 C NMR (100MHz, CDCl3), δ (ppm) : 137.32(C -α ), 122.02(C -β , C -γ ), 48.73(2 C -11 ), 46.04(2 C -2 ), 41.11(2 C -5 ), 38.58(2 C -6 ),38.05(2 C-1 ), 37.93(2 C -10 ), 33.35(2 C -7 ), 27.94(2 C -9 ), 26.09(2 C -4 ), 23.23(2C -8 ), 21.73(2 C -3 ); IR (KBr), ν max (cm -1 ): 3470, 3132, 3071, 2983, 2939, 2865,1652, 1627, 1563, 1506, 1468, 1384, 1366, 1269, 1223, 1115, 1085, 980, 955,866, 751.

[0087] Example 4: This example provides an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, R'M and R'Br are reacted, and the other aspects are the same as in Example 1 to obtain N,N'-bis-tetrahydrogeranyl imidazole bromide (R'-M-R'-Br), a light brown liquid, with a yield of 88%; its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 7-Figure 9 As shown; 1 H NMR (400MHz, CDCl3),δ (ppm) : 10.302(s, 1H, α- CH), 7.565(s, 2H, β- CH, γ- CH), 4.381(m, 4H, 2 1- CH2),1.938(m, 2H, 2 3- CH), 1.748(m, 2H, 2 7- CH), 1.497(m, 4H, 2 2- CH2), 1.297(m, 4H,2 4- CH2), 1.138(m, 8H, 2 5- CH2, 2 6- CH2), 0.972(d, J=6.4Hz, 6H, 2 9- CH3), 0.857(d, J=6.4Hz, 12H, 2 8- CH3, 2 10- CH3); 13 C NMR (100MHz, CDCl3), δ (ppm): 136.69(C -α ),122.19(C -β , C -γ ), 48.36(2 C -1 ), 39.00(2 C -2 ), 37.38(2 C -6 ), 36.86(2 C -4 ), 30.35(2C -3 ), 27.81(2 C -7 ), 24.46(2 C -5 ), 22.60(2 C -8 ), 22.48(2 C -10 ), 19.12(2 C -9 ); IR(liquid film), ν max (cm -1 ): 3132, 3065, 2955, 2927, 2869, 1717, 1625, 1563, 1515, 1466,1384, 1366, 1257, 1165, 1089, 981, 958, 865, 769.

[0088] Example 5: This example provides an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, R'M and R'Cl are reacted, and the other aspects are the same as in Example 1 to obtain N,N'-bis-tetrahydrogeranyl imidazole chloride (R'-M-R'-Cl), a light brown liquid, with a yield of 86.5%; its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 10-12 As shown; 1 H NMR (400MHz,CDCl3), δ (ppm) : 10.446(s, 1H, α- CH), 7.518(s, 2H, β- CH, γ- CH), 4.357(m, 4H, 2 1- CH2), 1.926(m, 2H, 2 3- CH), 1.739(m, 2H, 2 7- CH), 1.511(m, 4H, 2 2- CH2), 1.295(m, 4H, 2 4- CH2), 1.137(m, 8H, 2 5- CH2, 2 6- CH2), 0.975(d, J=6.4Hz, 6H, 29- CH3),0.862(d, J=6.4Hz, 12H, 2 8- CH3, 2 10- CH3); 13 C NMR (100MHz, CDCl3), δ (ppm) : 137.23(C -α ), 121.97(C -β , C -γ ), 48.28(2 C -1 ), 38.99(2 C -2 ), 37.36(2 C -6 ), 36.86(2 C -4 ),30.33(2 C -3 ), 27.81(2 C -7 ), 24.60(2 C -5 ), 22.59(2 C -8 ), 22.47(2 C -10 ), 19.20(2C -9 ); IR (liquid film), ν max (cm -1 ): 3391, 3136, 3091, 2955, 2928, 2870, 1714, 1642,1565, 1511, 1465, 1384, 1366, 1280, 1167, 1081, 959, 871, 731.

[0089] Example 6: This example provides an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, RM and R'Br are reacted (or R'M and RBr are reacted), and the other aspects are the same as in Example 1 to obtain N-hydrogenated nopyl-N'-tetrahydrogeranyl imidazole bromide (RM-R'-Br), a light brown viscous liquid, with a yield of 84%; its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 13-Figure 15 As shown; 1 H NMR (400MHz, CDCl3), δ (ppm) : 10.378(s, 1H, α- CH), 7.557(s, 2H, β- CH, γ- CH), 4.372(m, 4H, 11- CH2, 1'- CH2), 2.339(m, 1H, 2-CH), 2.032~1.846(m, 9H, 10- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2, 3'- CH), 1.738(m, 1H, 7'- CH), 1.513(m, 3H, 2'- CH2, 3- CH), 1.317(m, 2H, 4'- CH2), 1.184(s, 3H, 9- CH3), 1.132(m, 4H, 5'- CH2, 6'- CH2),1.016(s, 3H, 8- CH3), 0.971(d, J=6.4Hz, 3H, 9'- CH3), 0.865(d, J=6.4Hz, 7H, 8'- CH3, 10'- CH3, 7- CH); 13 C NMR (100MHz, CDCl3), δ (ppm) : 136.82(C -α ), 122.25, 122.12(C -β , C -γ ), 48.81(C -11 ), 48.36(C -1' ), 46.02(C -2 ), 41.12(C -5 ), 39.01(C -2' ), 38.59(C -6 ), 38.05(C -1 ), 37.97(C -10 ), 37.38(C -6' ), 36.89(C -4' ), 33.35(C -7 ), 30.37(C -3' ),27.95(C -9 ), 27.83(C -7' ), 26.09(C -4 ), 24.49(C -5' ), 23.25(C -8 ), 22.63, 22.50(C-8' , C -10' ), 21.77(C -3 ), 19.13(C -9' ); IR (liquid film), ν max (cm -1 ): 3427, 3129, 3057, 2962,2931, 2892, 1702, 1625, 1563, 1520, 1464, 1384, 1366, 1292, 1144, 1084, 957,866, 753.

[0090] Example 7: This example provides an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, RM and R'Cl or R'M and RCl are reacted, and the other aspects are the same as in Example 1 to obtain N-hydrogenated nopyl-N'-tetrahydrogeranyl imidazole chloride (RM-R'-Cl), a light brown viscous liquid, with a yield of 81.8%; its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 16-18 As shown; 1 H NMR (400MHz, CDCl3), δ (ppm) : 10.497(s, 1H, α- CH), 7.526(s, 2H, β- CH, γ- CH), 4.345(m, 4H, 11- CH2, 1'- CH2), 2.337(m, 1H, 2- CH), 2.043~1.838(m, 9H, 10- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2, 3'- CH), 1.738(m, 1H, 7'- CH), 1.511(m, 3H, 2'- CH2, 3- CH), 1.313(m, 2H, 4'- CH2), 1.180(s, 3H, 9- CH3), 1.130(m, 4H, 5'- CH2, 6'- CH2), 1.011(s,3H, 8- CH3), 0.978(d, J=6.4Hz, 3H, 9'-CH3), 0.864(d, J=6.4Hz, 7H, 8'- CH3, 10'- CH3, 7- CH); 13 C NMR (100MHz, CDCl3), δ (ppm) : 137.37(C -α ), 122.16, 122.05(C -β , C -γ ),48.80(C -11 ), 48.36(C -1' ), 46.06(C -2 ), 41.11(C -5 ), 39.00(C -2' ), 38.60(C -6 ), 38.06(C -1 ), 38.00(C -10 ), 37.41(C -6' ), 36.90(C -4' ), 33.35(C -7 ), 30.37(C -3' ), 27.94(C -9 ),27.82(C -7' ), 26.09(C -4 ), 24.48(C -5' ), 23.23(C -8 ), 22.62, 22.49(C -8' , C -10' ), 21.74(C -3 ), 19.10(C -9' ); IR (liquid film), ν max (cm -1 ): 3425, 3132, 3065, 2951, 2925, 2867,1639, 1562, 1509, 1467, 1383, 1366, 1279, 1165, 1087, 955, 871, 729.

[0091] Example 8: This example provides an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, RM is reacted with HK-Br, and the other aspects are the same as in Example 1 to obtain N-hydrogenated nopyl-N'-isobornyl methyl imidazole bromide (RM-HK-Br), a brown liquid with a yield of 78%. Its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 19-21 As shown;1 H NMR(400MHz, CDCl3), δ (ppm) : 10.411(s, 1H, α- CH), 7.592(s, 2H, β- CH, γ- CH), 4.376(m,2H, 11- CH2,), 4.253(m, 2H, 11'- CH2), 2.326(m, 1H, 2- CH), 2.147 (m, 1H, 1'- CH),2.035~1.845(m, 10H, 10- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2, 10'- CH2), 1.759(m, 1H, 4'- CH), 1.568(m, 3H, 2'- CH, 6'- CH2), 1.384~1.249(m, 5H, 5'- CH2, 7'- CH2, 3- CH,), 1.183(s, 3H, 9- CH3), 1.015(s, 3H, 8- CH3), 0.944(s, 3H, 9'- CH3), 0.883(d, J=9.6Hz, 1H, 7- CH b ); 0.842(s, 3H, 8'- CH3); 13 C NMR (100MHz, CDCl3), δ (ppm) : 134.81(C -α ), 120.38,120.23(C -β , C -γ ), 47.86(C -11 ), 46.83(C -11' ), 46.66(C -2 ), 45.41(C -1' ), 44.09(C -4' ),39.17(C -5 ), 38.58(C -2' ), 36.64(C-6 ), 36.02(C -10 ), 35.30(C -3' ), 35.00(C -10' ), 31.40(C -7 ), 30.26(C -9' ), 27.91(C -9 ), 26.00(C -7' ), 24.15(C -5 ), 22.54(C -6' ), 21.30(C -8 ),19.81(C -3 ), 19.52(C -8' ), 18.06(C -5' ); IR (liquid film), ν max (cm -1 ): 3412, 3130, 3057,2945, 2877, 1718, 1626, 1563, 1506, 1467, 1384, 1366, 1227, 1165, 1084, 954,875, 755, 644.

[0092] Example 9: This example provides an N,N'-bis-monoterpenoid imidazole quaternary ammonium salt. Specifically, R'M is reacted with HK-Br, and the other aspects are the same as in Example 1 to obtain N-tetrahydrogeranyl-N'-isobornylmethylimidazolium bromide (R'-M-HK-Br), a brown viscous liquid, with a yield of 81%. Its infrared spectrum, hydrogen spectrum and carbon spectrum are as follows: Figure 22-Figure 24 As shown; 1 H NMR (400MHz, CDCl3), δ (ppm) : 10.230(s, 1H, α- CH), 7.566(s, 2H, β- CH, γ- CH), 4.371(m,2H, 11- CH2,), 4.242(m, 2H, 1'- CH2), 2.150(br, 1H, 1- CH), 1.903(m, 3H, 10- CH2, 3'- CH), 1.756(m, 2H, 4- CH, 7'- CH), 1.620~1.480(m, 5H, 2- CH, 6- CH2,2'- CH2), 1.304(m,6H, 5- CH2, 7- CH2, 4'- CH2), 1.211~1.098(m, 4H, 5'- CH2, 6'- CH2), 0.977(d, J=6.8Hz,3H, 9'- CH3), 0.944(s, 3H, 9- CH3), 0.857(d, J=6.8Hz, 6H, 8'- CH3, 10'- CH3), 0.841(s,3H, 8- CH3); 13 C NMR (100MHz, CDCl3), δ (ppm) : 136.80(C -α ), 122.20(C -β , C -γ ), 49.80(C -11 ), 48.61(C -1 ), 48.34(C -1' ), 47.35(C -4 ), 40.51(C -2 ), 39.01(C -2' ), 37.37(C -3 ),37.22(C -6' ), 36.93(C -4' ), 36.85(C -10 ), 32.18(C -9 ), 30.33(C -3' ), 27.82(C -7' ), 27.58(C -7 ), 24.48(C -6 , C -5' ), 22.62(C -8' ), 22.49(C -10' ), 21.43(C -8 ), 19.97(C -5 ), 19.10(C -9' ); IR (neat film), ν max (cm -1): 3412, 3130, 3058, 2954, 2930, 2872, 1718, 1627,1563, 1510, 1464, 1384, 1366, 1280, 1166, 1084, 954, 876, 734, 662.

[0093] Antibacterial test: The mycelium growth rate method was used to prepare eight quaternary ammonium salt compounds with mass concentrations of 200, 100, 50, 25, 12.5, and 6.25 mg·L -1 The concentration of 100 μg / ml was used to test the antibacterial activity of 8 plant pathogenic fungi, including rice sheath blight (K), pine blight (S), tea fruit thorn spore (Cf), watermelon wilt (X), tobacco black shank (11), loquat anthracnose (P), velvet grass cover (V), and verticillium sphaeroides (O). The specific implementation method is as follows:

[0094] Under sterile conditions, DMSO was used as solvent and all eight compounds were prepared to a concentration of 200 mg / L -1 The solution was prepared into 100, 50, 25, 12.5, and 6.25 mg·L-1 by double dilution method. -1 , respectively, and added to potato dextrose agar (PDA) medium, with 3 replicates for each concentration. PDA medium with an equal amount of dimethyl sulfoxide added was used as a control. After inoculation, the bacterial cake was placed in a 25°C constant temperature incubator for culture. When the mycelium diameter of the control group reached more than 7 cm, the colony was measured by the cross method and photographed. The mycelium growth inhibition rate was calculated according to formula (1).

[0095] ;

[0096] The half inhibitory concentration (IC 50 ) value. Antibacterial data and IC values ​​of 8 quaternary ammonium compounds against 8 plant pathogens at 6 different concentrations 50 The values ​​are listed in Table 1, Table 2, Table 3 and Table 4 respectively.

[0097] ;

[0098] ;

[0099] ;

[0100] ;

[0101] From the data listed in the above four tables, it can be seen that the eight quaternary ammonium salt compounds have a relatively high inhibition rate against rice sheath blight (K), pine blight (S), watermelon wilt (X), and tobacco black shank (11). -1 When the concentration of the solution was 25 mg·L -1 The inhibition rate of 5 compounds against K bacteria exceeded 85%. The inhibition rate against pine blight pathogen (S) was -1 At the concentration of 100 mg·L -1 The inhibition rate of these six compounds can reach more than 89%. The inhibition rate of watermelon wilt pathogen (X) is 100 mg·L -1 When the concentration of the liquid was 50 mg·L -1 When the concentration was 200 mg·L -1 , there are 7 100%, the concentration is 100mg·L -1 When the concentration was 50 mg·L -1 When the concentration was 200 mg·L, 6 of them were higher than 80%. They all exceeded the inhibition rate of the positive control thiophanate-methyl against K, S, X, and 11 bacteria. Although the inhibition rate against Fusarium verticillioides (O) was not very high, it was still higher at a concentration of 200 mg·L -1 The inhibition rates of the eight compounds against O bacteria were all above 85%; at a concentration of 100 mg·L -1 When the IC 50 The values ​​were all lower than 25 mg·L -1 , 6 of which were below 20 mg·L -1 , 4 of which were below 15 mg·L -1 .

[0102] Based on the above-mentioned ideal embodiments of the present invention, the relevant staff can make various changes and modifications without departing from the technical concept of the present invention through the above-mentioned description. The technical scope of the present invention is not limited to the contents of the specification.

Claims

1. A method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salt, characterized in that: The following steps are involved: N-monoterpene imidazole and a halide containing a monoterpene group are added to an organic solvent for quaternization reaction, and then purified to obtain the N,N'-bis-monoterpene imidazole quaternary ammonium salt; the N-monoterpene imidazole is N-hydrogenated imidazole or N-tetrahydrogeranyl imidazole; the halide containing a monoterpene group is any one of hydrogenated imidazole bromide, hydrogenated imidazole chloride, tetrahydrogeranyl bromide, tetrahydrogeranyl chloride and isobornyl methyl bromide; The structural formula of N-hydrogenated imidazole is: ； The structural formula of N-tetrahydrogeranyl imidazole is: ； The structural formula of hydronopyl bromide is: ； The structural formula of hydronopyl chloride is: ； The structural formula of tetrahydrogeranyl bromide is: ； The structural formula of tetrahydrogeranyl chloride is: ； The structural formula of isobornylmethyl bromide is: 。 2. The method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salt according to claim 1, characterized in that: The organic solvent is at least one of ethanol, ethyl acetate, cyclohexane and acetonitrile.

3. The method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salt according to claim 1, characterized in that: The quaternization reaction method is a heating reflux reaction or a hydrothermal synthesis reaction.

4. The method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salt according to claim 1, characterized in that: The molar ratio of the N-monoterpene imidazole to the halide containing a monoterpene group is 1:(1-1.1).

5. The method for synthesizing N,N'-bis-monoterpenoid imidazole quaternary ammonium salt according to claim 1, characterized in that: The purification method comprises the following steps: after the reaction is completed, the organic solvent is evaporated, the residue is washed with petroleum ether, and after the organic solvent is removed, vacuum decompression treatment is performed to obtain the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt.

6. An N,N'-bis-monoterpenoid imidazole quaternary ammonium salt prepared by the synthesis method according to any one of claims 1 to 5.

7. The N,N'-bis-monoterpenoid imidazole quaternary ammonium salt according to claim 6, characterized in that: The N,N'-bis-monoterpenoid imidazole quaternary ammonium salt is any one of N,N'-dihydrogenated imidazole bromide, N,N'-dihydrogenated imidazole chloride, N,N'-di-tetrahydrogeranyl imidazole bromide, N,N'-di-tetrahydrogeranyl imidazole chloride, N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole bromide, N-hydrogenated imidazole-N'-tetrahydrogeranyl imidazole chloride, N-hydrogenated imidazole-N'-isobornylmethyl imidazole bromide, and N-tetrahydrogeranyl-N'-isobornylmethyl imidazole bromide.

8. Use of the N,N'-bis-monoterpenoid imidazole quaternary ammonium salt as claimed in claim 6 or 7 in resisting plant pathogens.

9. The use according to claim 8, characterized in that: The plant pathogens include rice sheath blight, pine blight, tea fruit thorn spore pathogen, watermelon wilt pathogen, tobacco black shank pathogen, loquat anthracnose pathogen, coriolus verticillaster, and fusarium wilt.

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