A synthetic method for hydrogenated nobylimidazolium-type quaternary ammonium salt compounds and its application

Abstract

This invention discloses a method for synthesizing hydrogenated nobylimidazole-type quaternary ammonium salt compounds and their applications, belonging to the field of natural product chemical synthesis technology. The method involves reacting hydrogenated nobyl bromide (chloride) with imidazole to obtain hydrogenated nobylimidazole. The hydrogenated nobylimidazole is then reacted with bromo(chloro)alkanes and α,ω-dihaloalkanes in a weakly polar solvent under heating. Gas chromatography analysis shows that after the reaction is complete, the solvent is distilled off, the distillation residue is washed with cyclohexane, the cyclohexane washings are separated, and the solvent is removed under reduced pressure to obtain the hydrogenated nobylimidazole-type quaternary ammonium salt compound. This method has the advantages of simple equipment, convenient operation, high product yield and purity, and reliable antibacterial properties.

Description

Technical Field

[0001] This invention relates to the field of natural product chemical synthesis technology, specifically to a method for synthesizing hydrogenated nobylimidazolium-type quaternary ammonium salt compounds and their applications. Background Technology

[0002] Plant diseases are a significant factor affecting plant growth, severely impacting agricultural production and economic benefits. 80% of plant diseases are caused by plant pathogens. Furthermore, plant pathogens can trigger a range of foodborne illnesses, seriously threatening human and animal health. Many researchers are focusing on and conducting research on the utilization of plant resources to control plant pathogens.

[0003] The mono- and di-quaternary ammonium salts containing hydrogenated nobutyl groups, obtained through chemical processing of β-pinene, one of the main components of turpentine, have good inhibitory effects on a variety of plant pathogens.

[0004] Imidazole quaternary ammonium salts are also a class of excellent cationic surfactants, which can be used as bactericides and are important raw materials for the preparation of liquid ionic compounds.

[0005] There are currently no reports on the synthesis methods of this type of hydrogenated nobylimidazolium quaternary ammonium salt compound or its antibacterial applications.

[0006] Therefore, there is a need to provide a method for synthesizing hydrogenated nobylimidazolium-type quaternary ammonium salt compounds and their applications, in order to solve the above problems. Summary of the Invention

[0007] In view of the shortcomings of the existing technology, the purpose of this invention is to provide a method for synthesizing hydrogenated nobylimidazolium quaternary ammonium salt compounds and their applications, so as to solve the problems in the background technology.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] A method for synthesizing a hydrogenated nobylimidazole type quaternary ammonium salt compound includes the following steps:

[0010] Step S1: Hydrogenated nobyl bromide (chloride) is reacted with imidazole to prepare hydrogenated nobyl imidazole;

[0011] In step S2, hydrogenated nobylimidazole reacts with bromo(chloro)alkanes and α,ω-dihaloalkanes in a weakly polar solvent under heat. Gas chromatography analysis shows that after the reaction is complete, the solvent is evaporated, the distillation residue is washed with cyclohexane, the cyclohexane washings are separated, and the solvent is removed under reduced pressure to obtain the hydrogenated nobylimidazole-type quaternary ammonium salt compound.

[0012] As a further aspect of the present invention, step S1 includes the following steps:

[0013] Step a1: Weigh 0.2 mol of hydrogenated norbutyl bromide (chloride), 0.21 mol of imidazole, 80 mL of ethanol and 8.0 g of sodium hydroxide and place them in an Erlenmeyer flask. Place the Erlenmeyer flask on a magnetic stirrer and install a reflux condenser on the Erlenmeyer flask. Stir, heat and reflux.

[0014] Step a2: After reflux for 8 hours, take samples and analyze them by gas chromatography to monitor the reaction. Stop the reaction when the content of hydrogenated nobyl bromide (chlorine) in the reaction solution is less than 5%.

[0015] Step a3: Cool the reaction solution, filter, evaporate the solvent from the filtrate by rotary evaporation, vacuum distill the remaining liquid, collect the distillate at 140℃ / 133Pa to obtain product 1, which is hydrogenated nobylimidazole;

[0016]

[0017] As a further aspect of the present invention, step S2 includes the following steps:

[0018] Step b1: Place 0.02 mol of product 1, 0.04 mol of bromo(chloro)alkanes and 30 mL of ethyl acetate in an Erlenmeyer flask, place the Erlenmeyer flask on a magnetic stirrer and heat to 70 °C for reaction;

[0019] Step b2: After reacting for 24 hours, take a sample, cool it, wash it with water, and analyze it by gas chromatography. If no product 1 is found, the reaction is complete.

[0020] Step b3: Ethyl acetate is removed by rotary evaporation of the reaction solution, and the distillation residue is washed with cyclohexane. The cyclohexane is separated and removed under reduced pressure to obtain the hydrogenated nobylimidazolium quaternary ammonium salt compound.

[0021]

[0022] As a further aspect of the present invention, step S2 includes the following steps:

[0023] Step c1: Place 0.02 mol of product 1, 0.01 mol of α,-dihaloalkane and 30 mL of ethyl acetate in an Erlenmeyer flask, place the Erlenmeyer flask on a magnetic stirrer and heat the mixture at 70 °C.

[0024] Step c2: After reacting for 24 hours, take a sample, cool it, wash it with water, and analyze it by gas chromatography. If no product 1 is found, the reaction is complete.

[0025] Step c3: Ethyl acetate is removed by rotary evaporation of the reaction solution, and the distillation residue is washed with cyclohexane to separate the cyclohexane. The cyclohexane is then removed under reduced pressure to obtain the hydrogenated nobylimidazolium quaternary ammonium salt compound.

[0026]

[0027] As a further embodiment of the present invention, the bromo(chloro)alkanes are one of bromoethane, bromopropane, bromobutane, 1-bromopentane, 1-bromohexane, 1-bromooctane, 1-bromodecane, chloropropane, chlorobutane, 1-chloropentane, 1-chlorohexane, 1-chlorooctane, and 1-chlorodecane.

[0028] As a further embodiment of the present invention, the α,ω-dihaloalkane is one of 1,2-dibromoethane, 1,2-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,10-dibromodecane, 1,12-dibromododecane, chloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, and 1,6-dichlorohexane.

[0029] As a further embodiment of the present invention, the molar ratio of the hydrogenated nobylimidazole to the haloalkane is 1:1.0-1.5, and the molar ratio of the hydrogenated nobylimidazole to α,ω-dihaloalkane is 2.1-2.5:1.

[0030] As a further embodiment of the present invention, the weakly polar solvent is ethyl acetate, acetone, and butanone.

[0031] Application of hydrogenated nobylimidazole quaternary ammonium salts, prepared according to the synthetic method of hydrogenated nobylimidazole quaternary ammonium salts, in inhibiting plant pathogenic fungi.

[0032] As a further aspect of the present invention, the plant pathogenic fungi include rice sheath blight pathogen, watermelon wilt pathogen, pine shoot blight pathogen, and loquat anthracnose pathogen.

[0033] In summary, the embodiments of the present invention have the following beneficial effects compared with the prior art:

[0034] This invention involves reacting hydrogenated nobyl bromide (chloride) with imidazole to obtain hydrogenated nobyl imidazole, followed by heating the hydrogenated nobyl imidazole with bromo(chloro)alkanes and α,ω-dihaloalkanes in a weakly polar solvent to finally obtain hydrogenated nobyl imidazole-type mono-quaternary ammonium salts and geminal quaternary ammonium salts. The equipment used in the reaction process is simple, the operation is convenient, and the product yield and purity are high. The obtained products have certain inhibitory effects on rice sheath blight pathogens, watermelon wilt pathogens, pine shoot blight pathogens, and loquat anthracnose pathogens. It has the advantages of simple equipment, convenient operation, high product yield and purity, and reliable antibacterial effect.

[0035] To more clearly illustrate the structural features and effects of the present invention, the present invention will be described in detail below with reference to specific embodiments. Detailed Implementation

[0036] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0037] The specific implementation of the present invention will be described in detail below with reference to specific embodiments.

[0038] In one embodiment of the present invention, the method for synthesizing a hydrogenated nobylimidazole type quaternary ammonium salt compound includes the following steps:

[0039] Step S1: Hydrogenated nobyl bromide (chloride) is reacted with imidazole to prepare hydrogenated nobyl imidazole;

[0040] In step S2, hydrogenated nobylimidazole reacts with bromo(chloro)alkanes and α,ω-dihaloalkanes in a weakly polar solvent under heat. Gas chromatography analysis shows that after the reaction is complete, the solvent is evaporated, the distillation residue is washed with cyclohexane, the cyclohexane washings are separated, and the solvent is removed under reduced pressure to obtain the hydrogenated nobylimidazole-type quaternary ammonium salt compound.

[0041] In this embodiment, step S1 includes the following steps: Step a1: Weigh 0.2 mol of hydrogenated nobyl bromide (chloride), 0.21 mol of imidazole, 80 mL of ethanol and 8.0 g of sodium hydroxide and place them in an Erlenmeyer flask. Place the Erlenmeyer flask on a magnetic stirrer and install a reflux condenser on the Erlenmeyer flask. Stir, heat and reflux. Step a2: After reflux for 8 hours, take a sample and analyze the reaction by gas chromatography. When the content of hydrogenated nobyl bromide (chloride) in the reaction solution is less than 5%, stop the reaction. Step a3: Cool the reaction solution, filter, evaporate the solvent from the filtrate by rotary evaporation, and vacuum distill the remaining liquid. Collect the distillate at 140℃ / 133Pa to obtain product 1, which is hydrogenated nobyl imidazole.

[0042]

[0043] Step S2 includes the following steps: Step b1, 0.02 mol of product 1, 0.04 mol of bromo(chloro)alkanes and 30 mL of ethyl acetate are placed in an Erlenmeyer flask, and the Erlenmeyer flask is placed on a magnetic stirrer and stirred, and heated to 70 °C for reaction; Step b2, after reacting for 24 h, a sample is taken, cooled, washed with water, and analyzed by gas chromatography. If no product 1 is found, the reaction is complete; Step b3, the ethyl acetate is removed by rotary evaporation of the reaction solution, the distillation residue is washed with cyclohexane, the cyclohexane is separated, and removed under reduced pressure to obtain the hydrogenated nobylimidazolium quaternary ammonium salt compound;

[0044]

[0045] Step S2 includes the following steps: Step c1, adding 0.02 mol of product 1 and 0.01 mol of α,

[0046] - Dihaloalkane and 30 mL of ethyl acetate were placed in an Erlenmeyer flask and stirred on a magnetic stirrer. The mixture was heated to 70 °C for reaction. Step c2: After 24 h of reaction, a sample was taken, cooled, washed with water, and analyzed by gas chromatography. If no product 1 was found, the reaction was complete. Step c3: The ethyl acetate was removed by rotary evaporation of the reaction solution. The distillation residue was washed with cyclohexane, and the cyclohexane was separated and removed under reduced pressure to obtain the hydrogenated nobylimidazolium quaternary ammonium salt compound.

[0047]

[0048] Wherein, the bromo(chloro)alkanes are one of bromoethane, bromopropane, bromobutane, 1-bromopentane, 1-bromohexane, 1-bromooctane, 1-bromodecane, chloropropane, chlorobutane, 1-chloropentane, 1-chlorohexane, 1-chlorooctane, and 1-chlorodecane;

[0049] The α,ω-dihaloalkane is one of 1,2-dibromoethane, 1,2-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,10-dibromodecane, 1,12-dibromododecane, chloropropane, 1,4-dichlorobutane, 1,5-dichloropentane, and 1,6-dichlorohexane;

[0050] The molar ratio of the hydrogenated nobylimidazole to the haloalkane is 1:1.0-1.5, and the molar ratio of the hydrogenated nobylimidazole to the α,ω-dihaloalkane is 2.1-2.5:1.

[0051] The weakly polar solvents are ethyl acetate, acetone, and butanone;

[0052] The heating method is reflux or hydrothermal synthesis reactor heating.

[0053] In Example 1, the preparation of hydrogenated nobylimidazole (product 1)

[0054] 0.2 mol of hydrogenated nobyl bromide (chloride), 0.21 mol of imidazole, 80 mL of ethanol, and 8.0 g of sodium hydroxide were placed in a 250 mL ground-glass conical flask. The flask was placed on a magnetic stirrer with a reflux condenser attached. The mixture was stirred, heated, and refluxed. After 8 hours, a sample was taken for gas chromatography analysis to monitor the reaction. The reaction was stopped when the hydrogenated nobyl bromide (chloride) content in the reaction solution was lower than 5%. The reaction solution was cooled, filtered, and the solvent was removed by rotary evaporation of the filtrate. The remaining liquid was vacuum distilled, and the distillate collected at 140 °C / 133 Pa was used to obtain product 1. The yield of product 1 was 92%, and the GC purity was 98.7%.

[0055] In Example 2, the general method for synthesizing N-hydronorbutyryl N'-alkylimidazolium bromide (2-14) was described.

[0056] 0.02 mol of hydrogenated nobylimidazole, 0.04 mol of bromo(chloro)alkanes, and 30 mL of ethyl acetate were placed in a 100 mL ground glass joint conical flask and stirred on a magnetic stirrer. The mixture was heated to 70 °C or in a hydrothermal synthesis reactor. After 24 h, a sample was taken, cooled, washed with water, and analyzed by gas chromatography. If no product 1 was found, the reaction was complete. The reaction solution was rotary evaporated to remove ethyl acetate. The distillation residue was washed with a small amount of cyclohexane to separate as much cyclohexane as possible. The residue was then removed under reduced pressure to obtain the product.

[0057] In Example 3, the bromo(chloro)alkanes were bromoethane, and the amount of bromoethane was 0.05 mol. The reaction was carried out in a hydrothermal synthesis reactor under heating conditions, and the rest was the same as in Example 2. N-hydronorbutyryl-N'-ethylimidazolium bromide (2) was obtained, which was a light brown viscous liquid with a yield of 79.5%.

[0058] 1 H NMR (400MHz, D2O), δ (ppm): 9.021 (s, 1H, 2’- CH), 7.589(s, 1H, 4’- CH), 7.548(s, 1H, 5’- CH), 4.228(t, J = 7.2H2, 4H, 12- CH 2,11- CH2), 2.181(m, 1H, 2- CH), 2.026~1.726(m,8H, 10- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH2), 1.467(t, J=7.2Hz, 4H, 3- CH, 13- CH3), 1.077(s, 3H, 8- CH3), 0.945(s, 3H), 9- CH3), 0.811 (d, J = 9.6 Hz, 1H), 7- CH).

[0059] 13 C NMR (100MHz, D2O), δ (ppm): 134.550 (C -2’ ),122.402(C -4’ ),122.287(C -5’ ),48.357(C -12),45.920(C -2 ),45.002(C -11 ),41.233(C -5 ),38.405(C -6 ),37.803(C -1 ),37.581(C -10 ),33.146(C -7 ),27.920(C -9 ),26.137(C -4 ),23.023(C -8 ),21.325(C -3 ),14.980(C -13 ).

[0060] IR (KBr tablets), ν max (cm -1 ):3423,3133,3062,2981,2940,2908,2866,1635,1564,1468,1384,1364,1167,766,649.

[0061] In Example 4, the bromo(chloro)alkanes were bromopropane, and the amount of bromopropane used was 0.04 mol. The reaction was carried out in a hydrothermal synthesis reactor under heating conditions, and the rest was the same as in Example 2. N-hydronorbutyryl-N'-n-propylimidazolium bromide (3) was obtained, which was a light brown viscous liquid with a yield of 78.4%.

[0062] 1 H NMR (400MHz, D2O), δ (ppm): 9.068 (s, 1H, 2’- CH), 7.597(s, 1H, 4’- CH), 7.000(s, 1H, 5’- CH), 4.186(m, 4H, 12- CH2, 11- CH2), 2.055(m, 1H, 2- CH), 1.929~1.704(m, 10H, 10- CH2, 5- CH, 7- CH, 1- CH, 3- CH, 4- CH 2,13- CH2), 1.464(m, 1H, 3- CH), 1.056(s, 3H, 8- CH3), 0.924(s, 3H, 9-CH3), 0.838(t, J=6.8Hz, 3H, 14- CH3),0.770(d,J=9.6Hz,1H,7-CH).

[0063] 13 C NMR (100MHz, D2O), δ (ppm): 135.455 (C -2’ ),122.716(C -4’ ),122.382(C -5’ ),51.201(C -12 ),48.387(C -11 ),45.940(C -2 ),41.260(C -5 ),38.379(C -6 ),37.781(C -1 ),37.595(C -10 ),33.170(C -7 ),27.911(C -9 ),26.121(C -4 ),23.034(C -8 ),22.892(C -13 ),21.314(C -3 ),10.131(C -14 ).

[0064] IR (KBr tablets), ν max (cm -1 ):3436,3131,3070,2964,2939,2910,2879,1629,1560,1466,1384,1366,1167,865,756,640.

[0065] In Example 5, the bromo(chloro)alkane was bromobutane, and the reaction was carried out in an Erlenmeyer flask. The rest of the reaction was the same as in Example 2, yielding N-hydronorbutyryl-N'-n-butylimidazolium bromide (4); a light brown viscous liquid with a yield of 84.3%.

[0066] 1 H NMR (400MHz, D2O), δ (ppm): 10.305 (s, 1H, 2’- CH), 7.611(s, 1H, 4’- CH), 7.501(s, 1H, 5’- CH), 4.387(m, 4H, 12- CH2, 11- CH2), 2.338(m, 1H, 2-CH), 1.922 (m, 10H, 10- CH2, 13- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2), 1.515 (m, 1H, 3- CH), 1.399 (m, 2H, 14- CH2), 1.184 (s, 3H, 8- CH3), 1.016 (s, 3H, 9- CH3), 0.965 (t, J=7.2 Hz, 3H, 15- CH3), 0.870 (d, J=9.6 Hz, 1H, 7- CH).

[0067] 13 C NMR (100 MHz, D2O), δ (ppm): 136.773 (C -2’ ), 122.375 (C -4’ ), 122.070 (C -5’ ), 49.771 (C -12 ), 48.802 (C -11 ), 46.015 (C -2 ), 41.118 (C -5 ), 38.604 (C -6 ), 38.057 (C -1 ), 37.902 (C -10 ), 33.369 (C -13 ), 32.152 (C -7 ), 27.952 (C -9 ), 26.095 (C -4 ), 23.262 (C -8 ), 21.778 (C -3 ), 19.423 (C -14 ), 13.446 (C -15 ).

[0068] IR (KBr pellet), ν max (cm -1 ): 3423, 3132, 3061, 2936, 2910, 2868, 1629, 1563, 1466, 1383, 1365, 1166, 753, 642.

[0069] In Example 6, the bromo(chloro)alkanes were 1-bromo-n-pentanes, and the reaction was carried out in an Erlenmeyer flask, with the other conditions being the same as in Example 2; N-hydronorbutyryl-N'-n-pentylimidazolium bromide (5) was obtained as a brown liquid with a yield of 81.4%.

[0070] 1 H NMR (400MHz, CDCl3), δ (ppm): 10.354 (s, 1H, 2’- CH), 7.620(s, 1H, 4’- CH), 7.538(s, 1H, 5’- CH), 4.382(m, 4H, 12- CH2, 11- CH2), 2.343(m, 1H, 2- CH), 1.944(m, 10H, 10- CH2, 13- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2), 1.523(m, 1H, 3- CH), 1.353(m, 4H, 14- CH2, 15- CH2), 1.182(s, 3H, 8- CH3), 1.015(s, 3H, 9- CH3), 0.893(t, J=6.8Hz, 3H, 16- CH3), 0.869 (d, J = 9.6 Hz, 1H), 7- CH).

[0071] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.775 (C -2’ ),122.350(C -4’ ),122.123(C -5’ ),49.995(C -12 ),48.796(C -11 ),42.020(C -2 ),41.108(C -5 ),38.594(C -6 ),38.039(C -1 ),37.943(C -10 ),33.349(C -7 ),29.940(C -13 ),28.197(C -14),27.942(C -9 ),26.085(C -4 ),23.256(C -8 ),22.009(C -15 ),21.765(C -3 ),13.809(C -16 ).

[0072] IR (KBr tablets), ν max (cm -1 ):3432,3131,3070,2935,2865,1629,1560,1468,1384,1366,1165,765,642.

[0073] In Example 7, the bromo(chloro)alkanes were 1-bromohexane, and the reaction was carried out in an Erlenmeyer flask, with the other steps being the same as in Example 2; N-hydronorbutyryl-N'-hexylimidazolium bromide (6) was obtained, a brown liquid with a yield of 86.1%.

[0074] 1 H NMR (400MHz, CDCl3), δ (ppm): 10.318 (s, 1H, 2’- CH), 7.586(s, 1H, 4’- CH), 7.521(s, 1H, 5’- CH), 4.376(t, J=6.4Hz, 4H, 12- CH 2,11- CH2), 2.338(m, 1H, 2- CH), 1.911(m, 10H, 10- CH2, 13- CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2), 1.522(m, 1H, 3- CH), 1.322(m, 6H, 14- CH2, 15- CH2, 16- CH2), 1.183(s, 3H, 8- CH3), 1.014(s, 3H, 9- CH3),0.870(t,J1=4.8Hz,J2=5.2Hz,4H, 17- CH3, 7- CH).

[0075] 13C NMR (100MHz, CDCl3), δ (ppm): 136.794 (C -2’ ),122.280(C -4’ ),122.117(C -5’ ),50.064(C -12 ),48.813(C -11 ),46.027(C -2 ),41.117(C -5 ),38.604(C -6 ),38.046(C -1 ),37.948(C -10 ),33.353(C -13 ),31.029(C -7 ),30.214(C -14 ),27.950(C -9 ),26.092(C -4 ),25.823(C -15 ),23.267(C -8 ),22.336(C -16 ),21.778(C -3 ),13.887(C -17 ).

[0076] IR (KBr tablets), ν max (cm -1 ):3436,3132,3074,2929,2862,2726,1628,1564,1468,1384,1366,1164,865,764,641.

[0077] In Example 8, the bromo(chloro)alkanes were 1-bromo-n-octane, and the reaction was carried out in an Erlenmeyer flask, with the other conditions being the same as in Example 2; N-hydronorbutyryl-N'-n-octylimidazolium bromide (7) was obtained as a brown liquid with a yield of 80.7%.

[0078] 1 H NMR (400MHz, CDCl3), δ (ppm): 10.427 (s, 1H, 2’- CH), 7.633(s, 1H, 4’- CH), 7.562(s, 1H, 5’- CH), 4.374(t, J = 7.2 Hz, 4H, 12- CH 2,11- CH2), 2.228(m, 1H, 2- CH), 1.921(m, 10H, 10- CH 2,13-CH2, 7- CH, 5- CH, 1- CH, 3- CH, 4- CH2), 1.489 (m, 1H, 3- CH), 1.245 (m, 10H, 14- CH2, 15- CH2, 16- CH2, 17- CH2, 18- CH2), 1.184 (s, 3H, 8-CH3), 1.017 (s, 3H, 9-CH3), 0.868 (t, J=6.4H2, 4H, 19- CH3, 7- CH).

[0079] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.799 (C -2’ ), 122.331 (C -4’ ), 122.187 (C -5’ ), 49.997 (C -12 ), 48.752 (C -11 ), 46.012 (C -2 I ), 41.094 (C -5 ), 38.580 (C -6 ), 38.022 (C -1 ), 37.958 (C -10 ), 33.335 (C -7 ), 31.592 (C -13 ), 30.285 (C -14 ), 28.969 (C -15 ), 28.890 (C -16 ), 27.924 (C -9 ), 26.173 (C -17 ), 26.075 (C -4 ), 23.245 (C -8 ), 22.495 (C -18 ), 21.749 (C -3 ), 13.990 (C -19 ).

[0080] IR (KBr pellet), ν max (cm<):3427,3133,3061,2925,2856,1624,1562,1467,1384,1366,1163,865,725,643.

[0081] In Example 9, the bromo(chloro)alkanes were 1-bromodecane, and the reaction was carried out in an Erlenmeyer flask, with the other conditions being the same as in Example 2; N-hydronorbutyryl-N'-decylimidazolium bromide (8) was obtained as a brown liquid with a yield of 82.3%.

[0082] 1 H NMR (400MHz, CDCl3), δ (ppm): 10.461 (s, 1H, 2’- CH), 7.564(s, 1H, 4’- CH), 7.520(s, 1H, 5’- CH), 4.364(t, J = 6.4 Hz, 4H, 12- CH 2,11- CH2), 2.326(m, 1H, 2- CH), 2.101~1.908(m,10H, 10- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH2, 13- CH2), 1.540(m, 1H, 3- CH), 1.331~1.245(m,14H, 14- CH2, 15- CH2, 16- CH2, 17- CH2, 18- CH2, 19- CH2, 20- CH2), 1.187(s, 3H, 8- CH3), 1.018(s, 3H, 9- CH3), 0.877(t, J = 6.8H2, 4H, 21- CH3, 7- CH).

[0083] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.956 (C -2’ ),122.213(C -4’ ),122.095(C -5’ ),50.042(C -12 ),48.797(C -11),48.027(C -2 ),41.116(C -5 ),38.615(C -6 ),38.050(C -1 ),37.980(C -10 ),33.367(C -7 ),31.787(C -13 ),30.325(C -14 ),29.413(C -15 ),29.358(C -16 ),29.200(C -17 ),28.980(C -18 ),27.950(C -9 ),26.219(C -19 ),26.101(C -4 ),23.280(C -8 ),22.608(C -20 ),21.783(C -3 ),14.071(C -21 ).

[0084] IR (KBr tablets), ν max (cm -1 ):3626,3131,3061,2925,2857,1632,1563,1511,1467,1384,1367,1229,1165,1109,1071,754,727,663.

[0085] In Example 10, the bromo(chloro)alkanes were chloropropane, and the reaction was carried out in a hydrothermal synthesis reactor under heating conditions, with the other conditions being the same as in Example 2; N-hydronorbutyryl-N'-n-propylimidazolium chloride (9) was obtained, a light brown liquid with a yield of 75.8%.

[0086] 1 H NMR (400MH2, CDCl3), δ (ppm): 8.850 (s, 1H, 2’- CH), 7.438(s, 1H, 4’- CH), 7.380(s, 1H, 5’- CH), 4.181(t, J = 7.2 Hz, 4H, 12- CH 2,11- CH2), 2.330(m, 1H, 2- CH), 1.973~1.822(m,10H, 10- CH 2,7- CH, 5- CH,1- CH, 3- CH, 4- CH 2,13- CH2), 1.488(m, 1H, 3- CH), 1.174(s, 3H, 8- CH3), 1.003(s, 3H, 9- CH3), 0.948(t, J=7.6Hz, 3H, 14- CH3), 0.874 (d, J = 9.2 Hz, 1H), 7- CH).

[0087] 13 C NMR (100MHz, CDCl3), δ (ppm): 135.589 (C -2’ ),122.531(C -4’ ),122.302(C -5’ ),51.446(C -12 ),48.821(C -11 ),45.954(C -2 ),41.154(C -5 ),38.626(C -6 ),38.092(C -1 ),37.781(C -10 ),33.375(C -7 ),27.950(C -9 ),26.137(C -4 ),23.462(C -13 ),23.152(C -8 ),21.612(C -3 ),10.526(C -14 ).

[0088] IR (KBr tablets), ν max (cm -1 ):3440,3133,3065,2939,1625,1617,1560,1466,1384,1367,1300,1166,1084,1059,893,643.

[0089] In Example 11, the bromo(chloro)alkanes were chlorobutane, and the reaction was carried out in a hydrothermal synthesis reactor under heating conditions, with the other conditions being the same as in Example 2; N-hydronorbutyryl-N'-n-butylimidazolium chloride (10) was obtained, a light brown liquid with a yield of 80.6%.

[0090] 1H NMR(400MHz,CDCl3),δ(ppm):10.704(s,1H, 2’- CH),7.704(s,1H, 4’- CH),7.548(s,1H, 5- CH),4.372(m,4H, 12- CH2, 11- CH2),2.328(m,1H, 2- CH),2.033~1.837(m,10H, 10- CH2, 7- CH, 5- CH, 1- CH, 13- CH2, 3- CH, 4- CH2),1.531(m,1H, 3- CH),1.394(m,2H, 14- CH2),1.180(s,3H, 8- CH3),1.013(s,3H, 9- CH3),0.961(t,J=7.2Hz,3H, 15- CH3),0.863(d,J=9.6Hz,1H, 7- CH).

[0091] 13 C NMR(100MHz,CDCl3),δ(ppm):137.354(C -2’ ),122.362(C -4’ ),121.954(C -5’ ),49.594(C -12 ),48.616(C -11 ),45.988(C -2 ),41.045(C -5 ),38.530(C -6 ),37.995(C -1 ),37.928(C -10 ),33.305(C -7 ),32.101(C -13 ),27.890(C -9 ),26.039(C -4 ),23.192(C -8 ),21.688(C -3 ),19.371(C -14 ),13.388(C -15 ).

[0092] IR (KBr tablets), ν max (cm -1 ):3428,3130,3062,2937,2868,1629,1562,1466,1384,1367,1166,866,753,644.

[0093] In Example 12, the bromo(chloro)alkanes were 1-chloro-n-pentane, and the reaction was carried out in an Erlenmeyer flask, with the other steps being the same as in Example 2; N-hydronorbutyryl-N'-n-pentylimidazolium chloride (11) was obtained, a brown liquid, with a yield of 86.1%.

[0094] 1 H NMR (400MHz, CDCl3), δ (ppm): 10.628 (s, 1H, 2’- CH), 7.678(s, 1H, 4’- CH), 7.562(s, 1H, 5’- CH), 4.369(m, 4H, 12- CH2, 11- CH2), 2.333(m, 1H, 2- CH), 2.016~1.836(m, 10H, 10- CH2, 7- CH, 5- CH, 13- CH2, 1- CH, 3- CH, 4- CH2), 1.523(m, 1H, 3- CH), 1.341(m, 4H, 14- CH2, 15- CH2), 1.179(s, 3H), 8- CH3), 1.012(s, 3H, 9- CH3), 0.889(t, J = 6.8 Hz, 3H, 16- CH3), 0.863 (d, J = 9.6 Hz, 1H), 7-CH ).

[0095] 13 C NMR (100MHz, CDCl3), δ (ppm): 137.264 (C -2’ ),122.283(C -4’ ),122.002(C -5’ ),49.834(C -12 ),48.620(C -11 ),45.987(C-2 ),41.038(C -5 ),38.522(C -6 ),37.979(C -1 ),37.905(C -1 ),33.294(C -7 ),29.878(C -13 ),28.153(C -14 ),27.881(C -9 ),26.030(C -4 ),23.180(C -8 ),21.959(C -3 ),21.668(C -15 ),13.752(C -16 ).

[0096] IR (KBr tablets), ν max (cm -1 ):3432,3129,3061,2935,2865,1631,1560,1468,1384,1367,1166,866,770,645.

[0097] In Example 13, the bromo(chloro)alkanes were 1-chlorohexane, and the reaction was carried out in an Erlenmeyer flask, with the other steps being the same as in Example 2; N-hydronorbutyryl-N'-hexylimidazolium chloride (12) was obtained, a brown liquid with a yield of 81.7%.

[0098] 1 H NMR (400MHz, CDCl3), δ (ppm): 10.455 (s, 1H, 4’- CH), 7.574(s, 1H, 4’- CH), 7.498(s, 1H, 5’- CH), 4.367(m, 4H, 12- CH2, 11- CH2), 2.342(m, 1H, 2- CH), 2.006~1.833(m,10H, 10- CH2, 7- CH, 5- CH, 1- CH, 4- CH2, 13- CH2), 1.523(m, 1H, 3- CH), 1.308(m, 6H, 14- CH 2,15- CH2, 16- CH2), 1.180(s, 3H,8- CH3), 1.010(s, 3H, 9- CH3), 0.867(t, J=7.2Hz, 4H, 7- CH, 17- CH3).

[0099] 13 C NMR (100MHz, CDCl3); δ (ppm): 137.239 (C -2’ ),122.154(C -4’ ),121.967(C -5’ ),49.980(C -12 ),48.728(C -11 ),46.020(C -2 ),41.087(C -5 ),38.574(C -6 ),38.022(C -1 ),37.941(C -10 ),33.341(C -7 ),31.035(C -13 ),30.193(C -14 ),27.918(C -9 ),26.077(C -4 ),25.826(C -15 ),23.228(C -8 ),22.329(C -16 ),21.717(C -3 ),13.882(C -17 ).

[0100] IR (KBr tablets), ν max (cm -1 ):3443,3130,3070,2934,2862,1631,1560,1466,1384,1366,1165,1115,866,765,642.

[0101] In Example 14, the bromo(chloro)alkanes were 1-chloro-n-octane, and the reaction was carried out in an Erlenmeyer flask, with the other conditions being the same as in Example 2; N-hydronorbutyryl-N'-n-octylimidazole chloride (13) was obtained, a brown liquid with a yield of 79.3%.

[0102] 1 H NMR (400MHz, CDCl3), δ (ppm): 10:486 (s, 1H, 2’- CH), 7.571(s, 1H, 4’-CH),7.506(s,1H, 5’- CH),4.365(t,J=7.2Hz,4H, 12- CH 2,11- CH2),2.328(m,1H, 2- CH),2.009~1.836(m,10H, 10- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH 2,13- CH2),1.538(m,1H, 3- CH),1.326~1.250(m,10H, 14- CH2, 15- CH2, 16- CH2, 17- CH2, 18- CH2),1.180(s,3H, 8- CH3),1.012(s,3H, 9- CH3),0.867(m,4H, 19- CH3, 7- CH).

[0103] 13 C NMR(100MHz,CDCl3),δ(ppm):137.285(C -2’ ),122.138(C -4’ ),121.988(C -5’ ),49.990(C -12 ),48.728(C -11 ),46.023(C -2 ),41.083(C -5 ),38.572(C -6 ),38.032(C -1 ),37.950(C -10 ),33.342(C -7 ),31.601(C -13 ),30.265(C -14 ),28.981(C -15 ),28.910(C -16 ),27.934(C -9 ),26.199(C -17 ),26.075(C -4 ),23.228(C -8 ),22.503(C-18 ),21.720(C -3 ),13.999(C -19 ).

[0104] IR (KBr tablets), ν max (cm -1 ):3432,3133,3062,2927,2859,1631,1560,1468,1386,1366,1164,1114,866,766,641.

[0105] In Example 15, the bromo(chloro)alkanes were 1-chloro-n-decane, and the reaction was carried out in an Erlenmeyer flask, with the other steps being the same as in Example 2; N-hydronorbutyryl-N'-n-decylimidazolium chloride (14) was obtained.

[0106] 1 H NMR (400MHz, CDCl3), δ (ppm): 10.497 (s, 1H, 2’- CH), 7.567(s, 1H, 4’- CH), 7.511(s, 1H, 5’- CH), 4.359(t, J = 7.2 Hz, 4H, 12- CH2, 11- CH2), 2.343(m, 1H, 2- CH), 2.008~1.848(m, 10H, 10- CH2, 7- CH, 5- CH, 1- CH,3-CH, 4- CH, 13- CH2), 1.489(m, 1H, 3- CH), 1.323~1.246(m,14H, 14- CH2, 15- CH2, 16- CH2, 17- CH 2,18- CH2, 19- CH2, 20- CH2), 1.181(s, 3H, 8- CH3), 1.012(s, 3H, 9- CH3), 0.874(t, J = 7.2 Hz, 4H, 7- CH, 21- CH3).

[0107] 13 C NMR (100MHz, CDCl3), δ (ppm): 137.289 (C-2’ ),122.119(C -4’ ),121.982(C -5’ ),49.975(C -12 ),48.708(C -11 ),466.030(C -2 ),41.091(C -5 ),38.567(C -6 ),38.042(C -1 ),37.943(C -10 ),33.338(C -7 ),31.746(C -13 ),30.262(C -14 ),29.375(C -15 ),29.326(C -16 ),29.158(C -17 ),28.958(C -18 ),27.920(C -9 ),26.206(C -19 ),26.074(C -4 ),23.215(C -8 ),22.565(C -20 ),21.717(C -3 ),14.027(C -21 ).

[0108] IR (KBr tablets), ν max (cm -1 ):3427,3131,3062,2925,2858,1632,1560,1467,1384,1367,1229,1165,1110,866,754,642.

[0109] In Example 16, a general method for synthesizing hydrogenated nobylimidazole-type geminal quaternary ammonium salts (15-24) was described.

[0110] 0.02 mol of hydrogenated nobylimidazole, 0.01 mol of α,-dihaloalkane and 30 mL of ethyl acetate were placed in a 100 mL ground glass conical flask and stirred at 70 °C. The reaction was carried out in the same manner as in Example 2 to obtain the product.

[0111] In Example 17, the dihaloalkane was 1,2-dibromoethane, and the rest was the same as in Example 16; dimethylene-1,2-bis(N-hydrogenated noripylimidazole bromide) (15) was obtained, a brown liquid with a yield of 80.1%.

[0112] 11H NMR (400 MHz Z , CDCl3), δ (ppm): 10.171 (s, 2H, 2 2’- CH), 8.513 (s, 2H, 2 4’- CH), 7.514 (s, 2H, 5’- CH), 5.282 (m, 4H, 2 12- CH2), 4.250 (m, 4H, 2 11- CH2), 2.323 (m, 2H, 2 2- CH), 1.902 [m, 16H, 2( 10- CH 2,7- CH,<00> 5- CH, 1- CH, 3- CH, 4- CH2)], 1.498 (m, 2H, 2 3- CH), 1.175 (s, 6H, 2 8- CH3), 1.014 (s, 6H, 2 9- CH3), 0.883 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0113] 13 13C NMR (100 MHz, CDCl3), δ (ppm): 136.737 (2C -2’ ), 124.084 (2C<>< / <>> -4’ ), 121.917 (2C -5’ ), 49.151 (2C -12 ), 48.173 (2C -11 ), 45.890 (2C -2 ), 41.049 (2C -5 ), 38.572 (2C -6 ), 37.954 (2C -1 , 2C -10 ), 33.305 (2C -7 ), 27.913 (2C -9 ), 26.018 (2C -4 ), 23.249 (2C -8 ), 21.724 (2C<00006> -3 ).

[0114] IR (KBr pellet), νmax (cm -1):3424,3133,3052,2984,2940,2902,2865,1632,1560,1468,1449,1384,1364,1171,637.

[0115] In Example 18, the dihaloalkane was 1,3-dibromopropane, and the rest was the same as in Example 16; a brown liquid, trimethylene-1,3-bis(N-hydrogenated noripylimidazole bromide) (16), was obtained with a yield of 83.6%.

[0116] 1 H NMR (400MH) Z ,CDCl3),δ(ppm):10.172(s,2H,2 2’- CH), 8.261(s,2H,2) 4’- CH), 7.457(s, 2H, 5’- CH), 4.725(m,4H,2 12- CH2), 4.307(m,4H,2) 11- CH2), 2.873(m,2H,2) 2- CH), 2.016[m, 18H, 2( 10- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH2), 13- CH2],1.530(m,2H,2 3- CH), 1.181(s, 6H, 2 8- CH3), 1.013(s, 6H, 2 9- CH3), 0.889 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0117] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.408 (2C -2’ ),123.314(2C -4’ ),121.795(2C -5’ ),48.933(2C -12 ),46.633(2C -11 ),45.893(2C -2 ),41.055(2C -5 ),38.564(2C -6 ),37.939(2C -1 ),37.618(2C -10),33.301(2C -7 ),30.869(2C -13 ),27.920(2C -9 ),26.038(2C -4 ),23.353(2C -8 ),21.724(2C -3 ).

[0118] IR (KBr tablet), νmax (cm) -1 ):3432,3132,3070,2985,2967,2937,2909,2885,1632,1559,1467,1453,1166,817,630.

[0119] In Example 19, the dihaloalkane was 1,4-dibromobutane, and the rest was the same as in Example 16; tetramethylene-1,4-bis(N-hydrogenated noroxymimidazolium bromide) (17) was obtained, a brown liquid with a yield of 86.7%.

[0120] 1 H NMR (400MH) Z ,CDCl3),δ(ppm):10.159(s,2H,2 2’- CH), 8.150(s,2H,2) 4’- CH), 7.375(s, 2H, 5’- CH), 4.600(m, 4H, 2 12- CH2), 4.279(m,4H,2) 11- CH2), 2.370(m,2H,2) 2- CH), 2.176~1.853[m,20H,2( 10- CH 2,13- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH2)],1.511(m,2H,2 3- CH), 1.182(s,6H,2) 8- CH3), 1.011(s, 6H, 2 9- CH3), 0.867 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0121] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.180 (2C -2’ ),123.661(2C-4’ ),121.239(2C -5’ ),48.815(2C -12 ),48.768(2C -11 ),45.951(2C -2 ),41.090(2C -5 ),38.593(2C -6 ),37.978(2C -1 ),37.774(2C -10 ),33.338(2C -7 ),27.949(2C -9 ),26.722(2C -13 ),26.076(2C -4 ),23.271(2C -8 ),21.746(2C -3 ).

[0122] IR (KBr tablet), νmax (cm) -1 ):3442,3133,3079,2983,2865,2719,1631,1559,1468,1384,1366,1164,865,758,630.

[0123] In Example 20, the dihaloalkane was 1,5-dibromopentane, and the rest was the same as in Example 16; pentamethylene-1,5-bis(N-hydrogenated noripylimidazole bromide) (18) was obtained, a brown liquid with a yield of 78.2%.

[0124] 1 H NMR (400MH) Z ,CDCl3),δ(ppm):9.320(s,2H,2 2’- CH), 8.674(s,2H,2) 4’- CH), 7.558(s, 2H, 5’- CH), 4.273(m,8H,2 12- CH2,2 11- CH2), 2.259(m,2H,2) 2- CH), 2.017~1.734[m,20H,2( 10- CH 2,13- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH2)],1.528(m,2H,2 14- CH2), 1.383(m,2H,2)3- CH), 1.146(s, 6H, 2 8- CH3), 1.009(s, 6H, 2 9- CH3), 0.855 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0125] 13 C NMR (100MHz, D2O), δ (ppm): 138.189 (2C -2’ ),125.398(2C -4’ ),126.312(2C -5’ ),52.074(2C -12 ),51.309(2C -11 ),48.083(2C -2 ),43.976(2C -5 ),41.123(2C -6 ),40.643(2C -1 ),40.412(2C -10 ),35.821(2C -7 ),31.498(2C -13 ),30.706(2C -9 ),28.871(2C -4 ),25.769(2C -8 ),25.041(2C -14 ),24.059(2C -3 ).

[0126] IR (KBr tablet), νmax (cm) -1 ):3432,3133,3074,2983,2940,2910,2865,1631,1563,1466,1384,1366,1164,638.

[0127] In Example 21, the dihaloalkane was 1,6-dibromohexane, and the rest was the same as in Example 16; hexamethylene-1,6-bis(N-hydrogenated noripylimidazole bromide) (19) was obtained, a brown liquid with a yield of 80.5%.

[0128] 1 H NMR (400MH) Z ,CDCl3),δ(ppm):10.268(s,2H,2 2’- CH), 8.004(s,2H,2) 4’- CH), 7.459(s, 2H, 5’- CH), 4.454(m,4H,212- CH2), 4.454 (m, 4H, 2 11- CH2), 2.313 (m, 2H, 2 2- CH), 2.047 [m, 20H, 2( 10- CH 2,13- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH2)], 1.468 (m, 6H, 2 3- CH, 2 14- CH2), 1.174 (s, 6H, 2 8- CH3), 1.009 (s, 6H, 2 9- CH3), 0.864 (d, J=9.6Hz, 2H, 2 7- CH).

[0129] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.451 (2C -2’ ), 123.216 (2C -4’ ), 121.741 (2C -5’ ), 49.371 (2C -12 ), 48.718 (2C -11 ), 45.978 (2C -2 ), 41.086 (2C -5 ), 38.550 (2C -6 ), 37.945 (2C -1 ), 37.848 (2C -10 ), 33.316 (2C -7 ), 29.416 (2C -13 ), 27.928 (2C -9 ), 26.048 (2C -4 ), 24.552 (2C -14 ), 23.236 (2C -8 ), 21.698 (2C -3 ).<000​​​​​​In Example 22, the dihaloalkane was 1,10-dibromodecane, and the rest was the same as in Example 16; decamethyl-1,10-bis(N-hydrogenated noroxymethylene imidazole bromide) (20) was obtained, a brown liquid with a yield of 75.8%.

[0132] 1 H NMR (400MH) Z ,CDCl3),δ(ppm):10.406(s,2H,2 2’- CH), 7.626(s,2H,2) 4’- CH), 7.547(s, 2H, 5’- CH), 4.366(m, 8H, 2 11- CH2,2 12- CH2), 2.333(m,2H,2 2- CH), 2.036~1.837[m,20H,2( 10- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH 2,13- CH2)],1.501(m,2H,2 3- CH), 1.329~1.247(m,12H,2) 14- CH2,2 15- CH2,2 16- CH2), 1.184(s, 6H, 2 8- CH3), 1.017(s, 6H, 2 9- CH3), 0.874 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0133] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.775 (2C -2’ ),122.264(2C -4’ 2C -5’ ),49.980(2C -12 ),48.739(2C -11 ),46.001(2C -2 ),41.092(2C -5 ),38.571(2C -6 ),38.021(2C -1 ),37.952(2C -10 ),33.330(2C -7 ),30.288(2C -13),29.369(2C -14 ),29.153(2C -15 ),28.940(2C -16 ),27.917(2C -9 ),26.070(2C -4 ),23.234(2C -8 ),21.738(2C -3 ).

[0134] IR (KBr tablet), νmax (cm) -1 ):3440,3133,3065,2925,2857,1641,1560,1466,1384,1365,1231,1165,1111,1079.

[0135] In Example 23, the dihaloalkane was 1,12-dibromododecane, and the rest was the same as in Example 16; dodecylmethylene-1,12-bis(N-hydrogenated noroxymethylenediazole bromide) (21) was obtained, a brown liquid with a yield of 79.3%.

[0136] 1 H NMR (400MH) Z ,CDCl3),δ(ppm):10.314(s,2H,2 2’- CH), 7.697(s,2H,2) 4’- CH), 7.533(s, 2H, 5’- CH), 4.384(m,8H,2 12- CH2,2 11- CH2), 2.328(m,2H,2) 2- CH), 2.029~1.855[m,20H,2( 10- CH 2,7- CH, 5- CH, 13- CH 2,1- CH, 3- CH, 4- CH2)],1.532(m,2H,2 3- CH), 1.335(m, 8H, 2 14- CH2,2 15- CH2), 1.240(s, 8H, 2 16- CH2,2 17- CH2), 1.181(s, 6H, 2 8- CH3), 1.014(s, 6H, 2 9- CH3), 0.868 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0137] 13 C NMR (100MHz, CDCl3), δ (ppm): 136.691 (2C -2’ ),122.529(2C -4’ ),122.121(2C -5’ ),49.967(2C -12 ),48.763(2C -11 ),46.030(2C -2 ),41.122(2C -5 ),38.619(2C -6 ),38.031(2C -1 ),37.977(2C -10 ),33.377(2C -7 ),30.207(2C -13 2C -14 ),28.972(2C -15 ),28.627(2C -16 ),27.980(2C -9 ),26.119(2C -4 ),23.293(2C -8 ),21.773(2C -3 ).

[0138] IR (KBr tablet), νmax (cm) -1 ):3440,3133,3065,2925,2857,1641,1560,1466,1384,1365,1231,1165,1111,1079.

[0139] In Example 24, the dihaloalkane was 1,4-dichlorobutane, and the rest was the same as in Example 16; tetramethylene-1,4-bis(N-hydrogenated noripylimidazole chloride) (22) was obtained, a light brown liquid with a yield of 84.7%.

[0140] 1 H NMR (400MH) Z ,D2O),δ(ppm):8.980(s,2H,2 2’- CH), 7.581(s,2H,2) 4’- CH), 7.496(s, 2H), 5’- CH), 4.258(m,4H,2 12- CH2), 4.191(s, 4H, 2 11- CH2), 2.130(m,2H,2) 2-CH), 1.931~1.742[m,20H,2( 10- CH 2,13- CH 2,7- CH, 5- CH, 1- CH, 3- CH, 4- CH2)],1.390(m,2H,2 3- CH), 1.030(s, 6H, 2 8- CH3), 0.895 (s, 6H, 2) 9- CH3), 0.670 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0141] 13 C NMR (100MHz, D2O), δ (ppm): 135.405 (2C -2’ ),122.657(2C -4’ ),122.595(2C -5’ ),48.787(2C -12 ),48.401(2C -11 ),45.800(2C -2 ),41.165(2C -5 ),38.301(2C -6 ),37.915(2C -1 ),37.664(2C -10 ),33.079(2C -7 ),27.935(2C -9 ),26.194(2C -4 ),26.069(2C -13 ),23.042(2C -8 ),21.194(2C -3 ).

[0142] IR (KBr tablet), νmax (cm) -1 ):3425,3135,3074,2983,2940,2866,1632,1564,1468,1384,1366,1164,758,634.

[0143] In Example 25, the dihaloalkane was 1,5-dichlorobutane, and the rest was the same as in Example 16; pentamethylene-1,5-bis(N-hydrogenated noroxymethylene chloride) (23) was obtained, a light brown liquid with a yield of 81.8%.

[0144] 1 H NMR (400MH)Z ,D2O),δ(ppm):8.963(s,2H,2 2’- CH),7.562(s,2H,2 4’- CH),7.503(s,2H, 5’- CH),4.202(m,8H,2 12- CH2,2 11- CH2),2.161(m,2H,2 2- CH),1.851[m,16H,2( 10- CH 2,13- CH 2,7- CH, 5- CH, 1- CH, 3- CH)],1.706(m,6H,2 4- CH2,2 3- CH),1.396(m,2H,2 3- CH),1.240(m,2H,2 14- CH2),1.027(s,6H,2 8- CH3),0.898(s,6H,2 9- CH3),0.729(d,J=9.6Hz,2H,2 7- CH).

[0145] 13 C NMR(100MHz,D2O),δ(ppm):135.355(2C -2’ ),122.548(2C -4’ ),122.469(2C -5’ ),49.227(2C -12 ),48.398(2C -11 ),46.775(2C -2 ),41.158(2C -5 ),38.228(2C -6 ),37.772(2C -1 ),37.408(2C -10 ),33.109(2C -7 ),28.880(2C -13 ),27.819(2C -9 ),26.042(2C -4 ),22.898(2C -8 ),22.181(2C -14 ),21.213(2C -3 ).

[0146] IR (KBr tablet), νmax (cm) -1 ):3425,3132,3072,2983,2939,2908,2865,1635,1564,1468,1384,1366,1165,754,640.

[0147] In Example 26, the dihaloalkane was 1,6-dichlorobutane, and the rest was the same as in Example 16; hexamethylene-1,6-bis(N-hydrogenated noripylimidazole chloride) (24) was obtained, a light brown liquid with a yield of 82.9%.

[0148] 1 H NMR (400MH) Z ,D2O),δ(ppm):8.947(s,2H,2 2’- CH), 7.563(s,2H,2) 4’- CH), 7.508(s, 2H, 5’- CH), 4.199(m, 8H, 2 12- CH2,2 11- CH2), 2.129(m,2H,2) 2- CH), 1.810[m, 14H, 2( 10- CH 2,13- CH 2,7- CH, 5- CH, 1- CH)],1.705(m,6H,2 3- CH,2 4- CH2), 1.392(m,2H,2) 3- CH), 1.240(m,4H,2 14- CH2), 1.019(s, 6H, 2 8- CH3), 0.887(s, 6H, 2) 9- CH3), 0.699 (d, J = 9.6 Hz, 2H, 2 7- CH).

[0149] 13 C NMR (100MHz, D2O), δ (ppm): 135.328 (2C -2’ ),122.723(2C -4’ ),122.537(2C -5’ ),49.340(2C -12 ),48.202(2C -11 ),45.921(2C -2 ),41.134(2C -5 ),38.288(2C -6),37.678(2C -1 ),37.441(2C -10 ),33.118(2C -7 ),29.253(2C -13 ),27.821(2C -9 ),26.023(2C -4 ),24.723(2C -14 ),22.888(2C -8 ),21.157(2C -3 );;.

[0150] IR (KBr tablet), νmax (cm) -1 ):3443,3133,3072,2983,2939,2865,1631,1563,1466,1384,1366,1165,763,640.

[0151] Antibacterial activity test

[0152] The inhibitory effects of 23 quaternary ammonium salts on four plant pathogens were tested using the mycelial growth rate method. The specific procedure was as follows: Under aseptic conditions, the compounds were prepared to a concentration of 0.024 mg·L⁻¹. -1 The solutions were added to sterilized potato dextrose agar medium at certain ratios to obtain final mass concentrations of 200, 100, 50, 25, and 12.5 mg·L⁻¹. -1 The culture medium plates containing the drug were prepared. A fungal disc, approximately 5 mm in diameter, was punched from the edge of a freshly cultured plant pathogen colony and inoculated into the center of each petri dish, repeated three times. Potato dextrose agar (PDA) plates without any added compounds served as a blank control group, and chlorothalonil as a positive control. The culture medium was stored in a 2°C incubator. When the colony diameter of the blank control group plates reached approximately 2 / 3 of the petri dish, the diameter of all cultured fungal colonies was measured using the cross-sectional method, and the average value was taken. The average diameter of fungal colonies in each petri dish was then calculated using the following formula: [Formula omitted for brevity].

[0153] Hyphae diameter = Average colony diameter - Diameter of the mycelial cake

[0154] Inhibition rate (%) = [(Control colony diameter - Treated colony diameter) / Control colony diameter] * 100%,

[0155] The names of the four plant pathogens are as follows: A. Rice sheath blight pathogen, B. Watermelon wilt pathogen, C. Pine shoot blight pathogen, and D. Loquat anthracnose pathogen;

[0156] The inhibition rate data of 23 hydrogenated nobylimidazolium quaternary ammonium salts against four plant pathogens are listed in Tables 1, 2, 3, and 4.

[0157] Table 1 shows the quaternary ammonium salt compounds at a drug concentration of 200 mg·L⁻¹. -1 At that time, 11 samples showed an antibacterial rate of over 90%, with 7 of them reaching 100%, all exceeding the levels of the commonly used fungicide chlorothalonil; the concentration was 100 mg·L⁻¹. -1 At that time, 6 samples showed an inhibition rate of 95%, with 4 of them reaching 100%; the concentration was 50 mg·L⁻¹. -1 At that time, four compounds showed an antibacterial rate of over 90%; compound 8 (RM-10-Br) showed an antibacterial rate of over 90% at a concentration of 12.5 mg·L⁻¹. -1 At that time, the inhibition rate against rice sheath blight was still as high as 97.5%, IC50 50 The value was 0.32, which is lower than that of carbendazim.

[0158] Table 2 shows the inhibition rate data of each compound against *Fusarium wilt* f. sp. 200 mg·L⁻¹. -1 At the specified concentration, 15 compounds showed an inhibition rate of over 90%, including 6 with 100% and 11 with over 95%; compounds 7 (RM-8-Br) and 13 (RM-8-Cl) showed inhibition rates of over 90% at a concentration of 12.5 mg·L⁻¹. -1 At that time, the inhibition rate against B bacteria remained above 90% (97.1%, 93.3%), of which IC50... 50 1.45 mg·L -1 and 1.43 mg·L -1 Compound 20((RM)2-10-BB)IC 50 The value is 1.59 mg·L. -1 Its antibacterial properties are also quite good.

[0159] Table 3 shows that these compounds generally exhibit good inhibitory effects against pine shoot blight pathogens, with a concentration of 200 mg·L⁻¹. -1 Thirteen compounds showed an inhibition rate of 100%, which was better than carbendazim (96.8%) at a concentration of 50 mg / L. -1 At that time, 5 compounds still had an inhibition rate of 100%, and a total of 13 compounds had an inhibition rate of over 85%; 11 compounds had an inhibition rate of 25 mg·L⁻¹. -1 At the specified concentration, its inhibition rate against C bacteria exceeded that of chlorothalonil at 200 mg·L⁻¹. -1 Inhibition rate against C bacteria; IC50 of compounds 7, 13, and 12 (RM-6-Cl) 50 Value below 3.0 mg·L -1 It has the best inhibitory effect on C bacteria;

[0160] As shown in Table 4, the 23 quaternary ammonium compounds generally exhibited low inhibitory rates against loquat anthracnose at a concentration of 200 mg / L. -1 At that time, only 7 compounds had an inhibition rate of more than 60%. Compounds 13, 7, 12 and 20 had the highest inhibition rate against D bacteria, and even exceeded the inhibition rate of chlorothalonil and carbendazim against D bacteria.

[0161] In terms of chemical structure, monoquaternary ammonium salts with alkyl groups of n-hexyl, n-octyl, and n-decyl, namely RM-6-Br, RM-8-Br, RM-10-Br, RM-6-Cl, RM-8-Cl, and RM-10-Cl, and geminal quaternary ammonium salts (RM)2-10-BB with ten methylene groups, showed stronger inhibitory effects on the tested plant pathogens.

[0162] Table 1. Inhibition rates (%) of 23 compounds against rice sheath blight pathogen.

[0163]

[0164]

[0165] Table 2. Inhibition rate (%) of 23 compounds against Fusarium wilt pathogen of watermelon.

[0166]

[0167]

[0168] Table 3. Inhibition rate (%) of 23 compounds against pine shoot blight pathogens

[0169]

[0170]

[0171] Table 4. Inhibition rates (%) of 23 compounds against *Anthracis japonicus* (loquat anthracnose)

[0172]

[0173]

[0174] As shown above, the quaternary ammonium compound 8 (N-hydronorbutyr-N′-n-decylimidazolium bromide) exhibited the highest inhibitory effect against rice sheath blight pathogen (A), with an inhibition rate as high as 97.5% and an IC50 value of 8.64 mg·L⁻¹ at a concentration of 12.5 mg / L. Compound 13 (N-hydronorbutyr-N′-n-octylimidazolium chloride) showed an inhibition rate of 89.6% and an IC50 value of 8.72 mg·L⁻¹ at a concentration of 25 mg·L⁻¹. Compound 7 (N-hydronorbutyr-N′-n-octylimidazolium bromide) also showed a significant inhibitory effect.At a concentration of 25 mg·L⁻¹, the inhibition rate was 81.6%, and the IC50 value was 8.64 mg·L⁻¹. Compound 20 (deca-methylene-1,10-bis(N-hydrogenated noroxymethylene-imidazolium bromide) in the gemini quaternary ammonium salt showed an inhibition rate of 89.6% at 50 mg·L⁻¹, with an IC50 value of 8.92 mg·L⁻¹. For *Fusarium wilt* (B), compounds 7 and 13 showed the highest inhibition rates. Compound 7 maintained a high inhibition rate of 97.1% at a concentration of 12.5 mg·L⁻¹, with an IC50 value of 1.45 mg·L⁻¹. Compound 13 showed the highest inhibition rate at a concentration of 12.5 mg·L⁻¹. The inhibition rate remained at 93.3%, and the IC50 value was 1.45 mg·L⁻¹. Gemini quaternary ammonium compound 20, at a concentration of 50 mg·L⁻¹, showed an inhibition rate of 86.7% and an IC50 value of 1.59 mg·L⁻¹. Regarding *Pinus pineus* causal agent (C), among the 23 compounds, 8 compounds had IC50 values ​​less than 4.2 mg·L⁻¹. Compounds 12 (N-hydronorbutyr-N′-n-hexylimidazole chloride), 13, 7, and 6 (N-norbutyr-N′-n-hexylimidazole bromide) showed the best inhibition against *Pinus pineus* causal agent C at a concentration of 12.5 mg·L⁻¹. The inhibition rates were 86%, 87.3%, 88.4%, and 84.9%, respectively, all higher than the inhibition rate of carbendazim against C at the same concentration (83.6%). Their IC50 values ​​were 2.26, 2.83, 2.96, and 4.18 (mg·L⁻¹), respectively. Compounds 8, 21 (dodecyl-1,12-bis(N-hydronorbutyrazole bromide), and 20 had IC50 values ​​(mg·L⁻¹) of 3.26, 3.46, and 3.94 against pathogen C, respectively. Compound 14 (N-hydronorbutyr-N′-n-decylimidazole bromide) had an IC50 value of 3.26, 3.46, and 3.94 against pathogen C. The O value was 4.30 mg·L⁻¹, and the inhibition rate was still above 80% at a concentration of 25 mg·L⁻¹. The inhibitory effect of the synthesized compounds on loquat anthracnose (D) was relatively weak. At a concentration of 200 mg·L⁻¹, only 9 compounds had an inhibition rate of more than 50%, and at a concentration of 100 mg·L⁻¹, only 5 compounds had an inhibition rate of more than 50%. Among them, the highest inhibition rates of compounds 13, 12 and 7 were 100, 89.1 and 88.0% respectively at a concentration of 200 mg·L⁻¹; and 76.1%, 58.9% and 69.9% respectively at a concentration of 100 mg·L⁻¹.

[0175] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for synthesizing a hydrogenated nobylimidazolium-type quaternary ammonium salt compound, characterized in that, Includes the following steps: Step S1: Hydrogenated norbutyl bromide or hydrogenated norbutyl chloride The reaction with imidazole yields hydrogenated nobylimidazole, i.e. ; Step S2: Hydrogenated nobylimidazole reacts with bromoalkanes or chloroalkanes in a weakly polar solvent under heat. Gas chromatography analysis shows that after the reaction is complete, the solvent is evaporated, the distillation residue is washed with cyclohexane, the cyclohexane washings are separated, and the solvent is removed under reduced pressure to obtain the hydrogenated nobylimidazole-type quaternary ammonium salt compound. The bromoalkane or chloroalkane is one of bromoethane, bromopropane, bromobutane, 1-bromopentane, 1-bromohexane, 1-bromooctane, 1-bromodecane, chloropropane, chlorobutane, 1-chloropentane, 1-chlorohexane, 1-chlorooctane, and 1-chlorodecane. Alternatively, hydrogenated nobylimidazole reacts with α,ω-dihaloalkanes in a weakly polar solvent upon heating. Gas chromatography analysis shows that after the reaction is complete, the solvent is distilled off, the distillation residue is washed with cyclohexane, the cyclohexane washings are separated, and the solvent is removed under reduced pressure to obtain the aforementioned hydrogenated nobylimidazole-type quaternary ammonium salt compound. The α,ω-dihaloalkane is one of 1,2-dibromoethane, 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, 1,6-dibromohexane, 1,10-dibromodecane, 1,12-dibromododecane, 1,4-dichlorobutane, 1,5-dichloropentane, and 1,6-dichlorohexane.

2. The method for synthesizing hydrogenated nobylimidazolium-type quaternary ammonium salt compounds according to claim 1, characterized in that, Step S1 includes the following steps: Step a1: Weigh 0.2 mol of hydrogenated norbutyl bromide or hydrogenated norbutyl chloride, 0.21 mol of imidazole, 80 mL of ethanol and 8.0 g of sodium hydroxide and place them in an Erlenmeyer flask. Place the Erlenmeyer flask on a magnetic stirrer and install a reflux condenser on the Erlenmeyer flask. Stir, heat and reflux. Step a2: After reflux for 8 hours, take samples and analyze them by gas chromatography to monitor the reaction. Stop the reaction when the content of hydrogenated nobyl bromide or hydrogenated nobyl chloride in the reaction solution is less than 5%. Step a3: Cool the reaction solution, filter, evaporate the solvent from the filtrate by rotary evaporation, and vacuum distill the remaining liquid to collect the distillate at 140℃ / 133Pa, which yields hydrogenated nobylimidazole. 。 3. The method for synthesizing hydrogenated nobylimidazolium-type quaternary ammonium salt compounds according to claim 2, characterized in that, Step S2 includes the following steps: Step b1: Place 0.02 mol of hydrogenated nobylimidazole, 0.04 mol of bromoalkanes or chloroalkanes and 30 mL of ethyl acetate in an Erlenmeyer flask, place the Erlenmeyer flask on a magnetic stirrer and heat to 70 °C for reaction. Step b2: After reacting for 24 hours, take a sample, cool it, wash it with water, and analyze it by gas chromatography. If no hydrogenated nobylimidazole is found, the reaction is complete. Step b3: Ethyl acetate is removed by rotary evaporation of the reaction solution, and the distillation residue is washed with cyclohexane. The cyclohexane is separated and removed under reduced pressure to obtain the hydrogenated nobylimidazolium quaternary ammonium salt compound. 。 4. The method for synthesizing hydrogenated nobylimidazolium-type quaternary ammonium salt compounds according to claim 2, characterized in that, Step S2 includes the following steps: Step c1: Place 0.02 mol of hydrogenated nobylimidazole, 0.01 mol of α,ω-dihaloalkane and 30 mL of ethyl acetate in an Erlenmeyer flask, place the Erlenmeyer flask on a magnetic stirrer and heat the mixture at 70 °C to react. Step c2: After reacting for 24 hours, take a sample, cool it, wash it with water, and analyze it by gas chromatography. If no hydrogenated nobylimidazole is found, the reaction is complete. Step c3: Ethyl acetate is removed by rotary evaporation of the reaction solution, and the distillation residue is washed with cyclohexane to separate the cyclohexane. The cyclohexane is then removed under reduced pressure to obtain the hydrogenated nobylimidazolium quaternary ammonium salt compound. 。 5. The method for synthesizing hydrogenated nobylimidazolium-type quaternary ammonium salt compounds according to claim 1, characterized in that, The molar ratio of the hydrogenated nobylimidazole to the bromoalkane or chloroalkane is 1:1.0-1.5, and the molar ratio of the hydrogenated nobylimidazole to the α,ω-dihaloalkane is 2.1-2.5:

1.

6. The method for synthesizing hydrogenated nobylimidazolium-type quaternary ammonium salt compounds according to claim 1, characterized in that, The weakly polar solvents are ethyl acetate, acetone, and butanone.

7. The application of hydrogenated nobylimidazolium quaternary ammonium salt compounds prepared by any one of the methods described in claims 1-6 in the inhibition of plant pathogenic fungi.

8. The application according to claim 7, characterized in that, The plant pathogenic fungi include rice sheath blight fungus, watermelon wilt fungus, pine shoot blight fungus, and loquat anthracnose fungus.

Images