Eugenol quaternary ammonium salt compound, preparation method and application in wood preservation

Abstract

The present invention provides a eugenol quaternary ammonium salt compound, a preparation method, and its application in wood preservation, relating to the technical field of organic chemistry. The present invention uses eugenol as a core skeleton, bridges a carbon chain with an alkyl tertiary amine, and forms a bromide salt. This salt significantly inhibits the growth of wood-decaying fungi. Furthermore, as a natural product, eugenol can avoid posing a threat to the ecological environment, thereby improving the safety and efficiency of the wood preservation process.

Description

Technical Field

[0001] The present invention relates to the technical field of organic chemistry, and in particular to a eugenol quaternary ammonium salt compound, a preparation method thereof, and application thereof in wood preservation. Background Art

[0002] Attacks by wood-decaying fungi are one of the main causes of wood biodegradation, severely impacting its durability and service life. This leads to resource waste, exacerbating the wood supply shortage, and undermining the sustainable development of the timber industry. Currently, chemical preservatives are the most widely used and convenient method for slowing wood biodegradation by fungi. However, existing chemical preservatives contain harmful metal elements (such as arsenic, chromium, and copper), and their extensive use poses a serious threat to the ecological environment. Therefore, the development of new, safe, and effective wood preservatives can help improve wood's resistance to wood decay fungi and extend its service life. Summary of the Invention

[0003] The present invention aims to provide a eugenol quaternary ammonium salt, a preparation method thereof and application thereof in wood preservation.

[0004] In a first aspect, the present invention provides a quaternary ammonium salt of eugenol as shown in Formula I:

[0005] ;

[0006] wherein v is any integer from 3 to 6, and the R group includes R-1 or R-2;

[0007] , ;

[0008] Here, m is any integer from 0 to 5, and n is any integer from 10 to 15.

[0009] Optionally, the structure comprises one of the following structural formulas:

[0010] ; ;

[0011] ;

[0012] ;

[0013] .

[0014] In a second aspect, the present invention also provides a method for preparing a quaternary ammonium salt of eugenol, comprising: introducing a dibromoalkane into eugenol under alkaline conditions to perform nucleophilic substitution to generate brominated eugenol, and introducing an alkyl tertiary amine ligand to perform a quaternization reaction to form a salt to obtain a quaternary ammonium salt of eugenol.

[0015] Optionally, the method comprises the following steps: reacting dibromoalkane with eugenol under alkaline conditions to generate brominated eugenol; and reacting brominated eugenol with an alkyl tertiary amine ligand to form a salt to obtain a quaternary ammonium salt of eugenol.

[0016] Alternatively, the reaction is carried out under alkaline conditions at 60°C-80°C.

[0017] Alternatively, the reaction is carried out under alkaline conditions for 36 h to 60 h.

[0018] Optionally, the molar ratio of the eugenol to the dibromoalkane is 1:(2-10).

[0019] Alternatively, after the reaction under alkaline conditions, the product is separated and impurities are removed and then purified by rotary evaporation and column chromatography to obtain bromoeugenol.

[0020] Alternatively, bromoeugenol is reacted with a tertiary alkylamine ligand at 20°C-30°C.

[0021] Alternatively, bromoeugenol is reacted with a tertiary alkylamine ligand for 1 h to 24 h.

[0022] Optionally, the molar ratio of the brominated eugenol to the alkyl tertiary amine ligand is 1:(1-5).

[0023] Optionally, after the reaction and salt formation, the eugenol quaternary ammonium salt is obtained by rotary evaporation and column chromatography purification.

[0024] Alternatively, the reaction formula for introducing dibromoalkane into eugenol for nucleophilic substitution to generate bromoeugenol is:

[0025] ;

[0026] Wherein, v is any integer from 3 to 6.

[0027] Alternatively, the reaction formula for preparing eugenol quaternary ammonium salt by introducing alkyl tertiary amine into the quaternization reaction is:

[0028] ;

[0029] Wherein, the R group includes R-1 or R-2;

[0030] , ;

[0031] Here, m is any integer from 0 to 5, and n is any integer from 10 to 15.

[0032] Optionally, the dibromoalkane includes one of 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane and 1,6-dibromohexane.

[0033] Optionally, the alkyl tertiary amine ligand includes one of N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, and N,N-dimethylhexadecylamine.

[0034] In a third aspect, the present invention also provides a use of a eugenol quaternary ammonium salt in wood preservation. BRIEF DESCRIPTION OF THE DRAWINGS

[0035] Figure 1 The structural formula of the eugenol quaternary ammonium salt provided by the present invention;

[0036] Figure 2 The present invention provides a flowchart of the method for preparing the eugenol quaternary ammonium salt. DETAILED DESCRIPTION

[0037] In order to make the purpose, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are 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 making creative work are within the scope of protection of the present invention. Unless otherwise defined, the technical terms or scientific terms used herein should be the common meanings understood by people with ordinary skills in the field to which the present invention belongs.

[0038] See also Figure 1 The present invention provides a quaternary ammonium salt of eugenol as shown in formula I, whose structural formula is:

[0039] ;

[0040] wherein v is any integer from 3 to 6, and the R group includes R-1 or R-2. In fact, the eugenol quaternary ammonium salt provided by the present invention uses eugenol as a core skeleton, which, as a natural product, has the advantages of low toxicity and side effects, reproducibility, and low cost.

[0041] Specifically, the structural formula of the R-1 group is:

[0042] ;

[0043] Here, m is any integer from 0 to 5.

[0044] Specifically, the structural formula of the R-2 group is:

[0045] ;

[0046] Wherein, n is any integer from 10 to 15.

[0047] In some embodiments, the structure of the eugenol quaternary ammonium salt provided by the present invention includes one of the following structural formulas:

[0048] ; ;

[0049] ;

[0050] ;

[0051] .

[0052] The present invention also provides a method for preparing a quaternary ammonium salt of eugenol, comprising: introducing a dibromoalkane into eugenol under alkaline conditions for nucleophilic substitution to produce brominated eugenol; and introducing an alkyl tertiary amine ligand for quaternization to form a salt to obtain the quaternary ammonium salt of eugenol. In practice, the introduction of the dibromoalkane for nucleophilic substitution allows the introduction of carbon chains of varying lengths into eugenol, and the introduction of bromine to form a bromide salt in the subsequent salt formation process.

[0053] In some embodiments, see Figure 2 The preparation method provided by the present invention comprises the following steps:

[0054] S1. reacting a dibromoalkane with eugenol under alkaline conditions to generate bromoeugenol;

[0055] S2. Reacting bromoeugenol with an alkyl tertiary amine ligand to form a salt to obtain eugenol quaternary ammonium salt.

[0056] In practice, step S1 can be carried out under alkaline conditions at 60°C-80°C for 36-60 hours. Furthermore, the molar ratio of eugenol to dibromoalkane used in the reaction is 1:(2-10). Specifically, after the reaction is completed in step S1, the product is separated and impurities removed, and then purified by rotary evaporation and column chromatography to obtain bromoeugenol.

[0057] In step S2, the bromoeugenol and the alkyl tertiary amine ligand are reacted at 20°C-30°C for 1-24 hours until the reaction is complete. Furthermore, the molar ratio of the bromoeugenol to the alkyl tertiary amine ligand is 1:(1-5). After the reaction and salt formation, the eugenol quaternary ammonium salt is purified by rotary evaporation and column chromatography.

[0058] Specifically, in step S1, the reaction formula for introducing dibromoalkane into eugenol for nucleophilic substitution to generate bromoeugenol is:

[0059] .

[0060] Specifically, in step S2, the reaction formula for preparing eugenol quaternary ammonium salt by introducing alkyl tertiary amine into the quaternization reaction is:

[0061] .

[0062] In some embodiments, the dibromoalkane used includes one of 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, and 1,6-dibromohexane, and the alkyl tertiary amine ligand used includes one of N-methyldiethanolamine, N-ethyldiethanolamine, N-butyldiethanolamine, N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, and N,N-dimethylhexadecylamine.

[0063] In fact, the present invention also provides an application of eugenol quaternary ammonium salt in wood preservation.

[0064] Preparation Example 1

[0065] Preparation Example 1 provides a method for synthesizing bromoeugenol, comprising the following steps: stirring 100 mmol of eugenol (CAS: 97-53-0) and 200 mmol of anhydrous potassium carbonate in 200 mL of acetone for 30 minutes, slowly adding dropwise 500 mmol of 1,3-dibromopropane (CAS: 109-64-8), and stirring in a 70°C water bath for 48 hours until the reaction is complete; removing the potassium carbonate by filtration, and then desolvating by rotary evaporation. The product is purified by silica gel column chromatography (petroleum ether:ethyl acetate = 10:1) to obtain bromoeugenol II-1 as a yellow liquid, with a calculated yield of 80%.

[0066]

[0067] The data of H NMR spectrum of bromoeugenol II-1 are: 1 H NMR (400 MHz, DMSO-d6) δ 6.89(d, J = 8.1 Hz, 1H), 6.79 (d, J = 1.8 Hz, 1H), 6.72 – 6.61 (m, 1H), 5.94(ddt, J = 16.8, 10.0, 6.7 Hz, 1H), 5.05 (ddd, J = 12.0, 9.5, 1.4 Hz, 2H), 4.02 (t, J = 6.0 Hz, 2H), 3.74 (s, 3H), 3.66 (t, J = 6.5 Hz, 2H), 3.29 (d, J= 6.7 Hz, 2H), 2.21 (p, J = 6.3 Hz, 2H).

[0068] Preparation Example 2

[0069] Preparation Example 2 provides a method for synthesizing bromoeugenol. The method differs from Preparation Example 1 in that 500 mmol of 1,4-dibromobutane (CAS: 110-52-1) is slowly added dropwise to obtain bromoeugenol II-2 as a yellow liquid after purification, with a calculated yield of 78%.

[0070]

[0071] The data of H NMR spectrum of bromoeugenol Ⅱ-2 are: 1 H NMR (400 MHz, CDCl3) δ 6.80(d, J = 8.4 Hz, 1H), 6.70 (d, J = 7.2 Hz, 2H), 5.95 (ddt, J = 16.8, 10.0, 6.7Hz, 1H), 5.07 (dd, J = 13.2, 7.1 Hz, 2H), 4.02 (t, J = 6.1 Hz, 2H), 3.84 (s,3H), 3.49 (t, J = 6.6 Hz, 2H), 3.33 (d, J = 6.6 Hz, 2H), 2.12 – 2.03 (m, 2H),2.01 – 1.92 (m, 2H).

[0072] Preparation Example 3

[0073] Preparation Example 3 provides a method for synthesizing bromoeugenol. The difference from Preparation Example 1 is that 500 mmol of 1,5-dibromopentane (CAS: 111-24-0) is slowly added dropwise to obtain bromoeugenol II-3 as a yellow liquid after purification, with a calculated yield of 82%.

[0074]

[0075] The data of H NMR spectrum of bromoeugenol II-3 are: 1H NMR (400 MHz, CDCl3) δ 6.80(d, J = 8.4 Hz, 1H), 6.70 (d, J = 7.2 Hz, 2H), 5.95 (ddt, J = 16.8, 10.0, 6.7Hz, 1H), 5.12 – 5.01 (m, 2H), 4.04 – 3.95 (m, 2H), 3.84 (s, 3H), 3.43 (t, J =6.8 Hz, 2H), 3.33 (d, J = 6.7 Hz, 2H), 1.98 – 1.89 (m, 2H), 1.89 – 1.81 (m,2H), 1.66 – 1.57 (m, 2H).

[0076] Preparation Example 4

[0077] Preparation Example 4 improves the synthesis method of bromoeugenol. The difference from Preparation Example 1 is that 500 mmol of 1,6-dibromohexane (CAS: 629-03-8) is slowly added dropwise to obtain bromoeugenol II-4 as a yellow liquid after purification. The calculated yield is 82%.

[0078]

[0079] The data of H NMR spectrum of bromoeugenol II-4 are as follows: 1 H NMR (400 MHz, CDCl3) δ 6.79(d, J = 7.9 Hz, 1H), 6.69 (d, J = 7.6 Hz, 2H), 5.95 (ddt, J = 16.8, 10.0, 6.7Hz, 1H), 5.11 – 5.01 (m, 2H), 3.98 (q, J = 6.9 Hz, 2H), 3.83 (s, 3H), 3.39 (t, J = 6.8 Hz, 2H), 3.32 (d, J = 6.7 Hz, 2H), 1.85 (dp, J = 20.2, 6.8 Hz,4H), 1.56 – 1.41 (m, 4H).

[0080] Example 1

[0081] This Example 1 provides a method for preparing a eugenol quaternary ammonium salt, comprising the following steps: adding 15 mmol of N-methyldiethanolamine (CAS: 105-59-9) to 10 mL of acetonitrile and stirring to dissolve, adding 5 mmol of bromoeugenol II-1 (Preparation Example 1), stirring at 25° C. until the reaction is complete (TLC monitoring), and then removing the solvent by rotary evaporation and purifying by column chromatography to obtain a yellow oily eugenol quaternary ammonium salt I-1 (3-(4-allyl-2-methoxyphenoxy)-N,N-bis(2-hydroxyethyl)-N-methylpropane-1-ammonium bromide) (1 L), with a calculated yield of 82%.

[0082]

[0083] The characterization data of eugenol quaternary ammonium salt Ⅰ-1 (1L) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.89 (d, J = 8.1 Hz, 1H), 6.79 (s, 1H), 6.67 (d, J = 8.0 Hz, 1H), 5.97 – 5.89 (m, 1H), 5.04 (dd, J = 25.8, 13.5 Hz, 2H), 3.96 (t, J = 6.2 Hz,2H), 3.85 (s, 4H), 3.74 (s, 3H), 3.62 (t, J = 5.6 Hz, 2H), 3.55 – 3.48 (m,6H), 3.28 (d, J = 6.5 Hz, 2H), 3.14 (s, 3H), 1.87 (dt, J = 15.2, 5.3 Hz, 2H),1.75 – 1.69 (m, 2H); 13 C NMR (151 MHz, DMSO-d6) δ 150.19, 146.90, 138.82,134.21, 121.28, 116.52, 115.45, 113.72, 67.09, 64.43, 60.79, 59.34, 57.78,56.59, 55.72, 50.23, 42.48, 40.01, 23.37. HRMS (ESI, m / z): [M-Br] + Calcd for C 18 H 30 BrNO4: 324.2169; found: 324.21584.

[0084] Example 2

[0085] This Example 2 provides a method for preparing a eugenol quaternary ammonium salt, which differs from Example 1 in that 15 mmol of N-butyldiethanolamine (CAS: 102-79-4) is added to 10 mL of acetonitrile and stirred for dissolution; after purification, a yellow solid eugenol quaternary ammonium salt I-2 (N-(3-(4-allyl-2-methoxyphenoxy)propyl)-N,N-bis(2-hydroxyethyl)butyl-1-ammonium bromide) (1M) is obtained, with a calculated yield of 90%.

[0086]

[0087] The characterization data of eugenol quaternary ammonium salt Ⅰ-2 (1M) were as follows: M. p.: 79.4-81.4℃; 1H NMR (600 MHz, DMSO-d6) δ 6.94 (d, J = 8.0 Hz, 1H), 6.84 (s, 1H), 6.73 (d,J = 7.7 Hz, 1H), 6.02 – 5.93 (m, 1H), 5.29 (s, 2H), 5.09 (dd, J = 23.4, 13.5Hz, 2H), 4.02 (s, 2H), 3.87 (s, 4H), 3.79 (s, 3H), 3.53 (d, J = 18.6 Hz, 6H),3.43 (d, J = 7.3 13C NMR (151) MHz, DMSO-d6) δ 150.04, 146.79, 138.78, 134.03, 121.19, 116.44, 115.03, 113.60,66.56, 61.15, 60.16, 57.42, 56.50, 55.48, 39.96, 24.00, 22.83, 20.00, 14.37.HRMS (ESI, m / z): [M-Br]+ Calcd for C21H36BrNO4: 366.2639; found: 366.26283.

[0088] Example 3

[0089] This Example 3 provides a preparation method of eugenol quaternary ammonium salt, which differs from Example 1 in that 15 mmol of N,N-dimethyldodecylamine (CAS: 112-28-7) is added to 10 mL of acetonitrile and stirred for dissolution; after purification, eugenol quaternary ammonium salt I-3 (N-(3-(4-allyl-2-methoxyphenoxy)propyl)-N,N-dimethyldodecyl-1-ammonium bromide) (1N) is obtained in the form of brown syrup, with a calculated yield of 90%.

[0090]

[0091] The characterization data of eugenol quaternary ammonium salt Ⅰ-3 (1N) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.96 (dd, J = 10.2, 8.6 Hz, 1H), 6.81 (s, 1H), 6.69 (d, J = 7.9Hz, 1H), 6.00 – 5.90 (m, 1H), 5.05 (dd, J = 26.7, 13.5 Hz, 2H), 4.03 (s, 2H), 3.77 (s, 3H), 3.51 (d, J = 6.7 Hz, 2H), 3.43 – 3.37 (m, 2H), 3.30 (d, J = 6.1Hz, 2H), 3.15 (s, 6H), 2.16 (s, 2H), 1.68 (s, 2H), 1.24 (s, 18H), 0.85 (t, J= 6.0 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ 150.18, 146.79, 138.71, 134.13,121.21, 116.32, 115.51, 113.60, 66.96, 63.86, 61.15, 56.53, 51.24, 40.03,32.24, 30.00, 29.98, 29.93, 29.83, 29.67, 29.49, 26.71, 23.47, 23.03, 22.67,14.78. HRMS (ESI, m / z): [M-Br] + Calcd for C 27 H 48 BrNO2: 418.3680; found:418.36751.

[0092] Example 4

[0093] This Example 4 provides a method for preparing a eugenol quaternary ammonium salt, which differs from Example 1 in that 15 mmol of N,N-dimethyltetradecylamine (CAS: 3015-65-4) is added to 10 mL of acetonitrile and stirred for dissolution; after purification, eugenol quaternary ammonium salt I-4 (N-(3-(4-allyl-2-methoxyphenoxy)propyl)-N,N-dimethyltetradecyl-1-ammonium bromide) (1O) is obtained in the form of brown syrup, with a calculated yield of 90%.

[0094]

[0095] The characterization data of eugenol quaternary ammonium salt Ⅰ-4 (1O) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.95 (d, J = 8.1 Hz, 1H), 6.83 (s, 1H), 6.71 (d, J = 7.9 Hz, 1H), 6.00 – 5.92 (m, 1H), 5.06 (dd, J = 26.1, 13.2 Hz, 2H), 4.03 (s, 2H), 3.78 (s,3H), 3.41 – 3.36 (m, 2H), 3.32 (d, J = 5.9 Hz, 2H), 3.14 (s, 6H), 2.16 (s,2H), 1.69 (s, 2H), 1.25 (s, 24H), 0.87 (t, J = 5.9 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ 150.19, 146.78, 138.72, 134.15, 121.20, 116.35, 115.50, 113.61, 66.96, 63.85, 61.18, 56.49, 51.21, 40.01, 32.22, 30.00, 29.97, 29.95, 29.80,29.64, 29.46, 26.69, 23.43, 23.00, 22.63, 14.78. HRMS (ESI, m / z): [M-Br] + Calcd for C 29 H 52 BrNO2: 446.3993; found: 446.39900.

[0096] Example 5

[0097] This Example 5 provides a method for preparing a eugenol quaternary ammonium salt, which differs from Example 1 in that 15 mmol of N,N-dimethylhexadecylamine (CAS: 3886-91-7) is added to 10 mL of acetonitrile and stirred for dissolution; after purification, eugenol quaternary ammonium salt I-5 (N-(3-(4-allyl-2-methoxyphenoxy)propyl)-N,N-dimethylhexadecyl-1-ammonium bromide) (1P) is obtained in the form of brown syrup, with a calculated yield of 92%.

[0098]

[0099] The characterization data of eugenol quaternary ammonium salt Ⅰ-5 (1P) by NMR hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.95 (d, J = 8.0 Hz, 1H), 6.82 (s, 1H), 6.70 (d, J = 7.8 Hz, 1H), 5.94 (dq, J = 8.2, 6.9 Hz, 1H), 5.05 (dd, J = 27.2, 13.4 Hz, 2H), 4.03 (s,2H), 3.77 (s, 3H), 3.53 (d, J = 4.4 Hz, 2H), 3.39 (d, J = 7.7 Hz, 2H), 3.31(d, J = 6.1 Hz, 2H), 3.15 (s, 6H), 2.16 (s, 2H), 1.69 (s, 2H), 1.24 (s, 26H), 0.86 (t, J = 6.2 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ 149.71, 146.33, 138.25,133.63, 120.73, 115.84, 115.01, 113.10, 66.49, 63.34, 60.65, 56.02, 50.76,39.58, 31.81, 29.60, 29.54, 29.42, 29.24, 29.07, 26.27, 22.99, 22.58, 22.20,14.30. HRMS (ESI, m / z): [M-Br] + Calcd for C 31 H 56 BrNO2: 474.4306; found:474.43059.

[0100] The synthetic reaction formulas of the eugenol quaternary ammonium salts provided in Examples 1 to 5 are shown in Table 1 below.

[0101] Table 1 Synthesis reaction formula of eugenol quaternary ammonium salt in Examples 1 to 5

[0102]

[0103] Example 6 to Example 10

[0104] Examples 6 to 10 provide a method for preparing a eugenol quaternary ammonium salt, respectively. The types of brominated eugenol and alkyl tertiary amine ligands used, and the structural formulas of the eugenol quaternary ammonium salts obtained are shown in Table 2 below.

[0105] Table 2 Structural formulas of brominated eugenol, alkyl tertiary amine ligands, and eugenol quaternary ammonium salts in Examples 6 to 10

[0106]

[0107] The characterization data of eugenol quaternary ammonium salt Ⅰ-6 (2L) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.89 (d, J = 8.1 Hz, 1H), 6.79 (s, 1H), 6.67 (d, J = 8.0 Hz, 1H), 5.97 – 5.89 (m, 1H), 5.04 (dd, J = 25.8, 13.5 Hz, 2H), 3.96 (t, J = 6.2 Hz,2H), 3.85 (s, 4H), 3.74 (s, 3H), 3.62 (t, J = 5.6 Hz, 2H), 3.55 – 3.48 (m,6H), 3.28 (d, J = 6.5 Hz, 2H), 3.14 (s, 3H), 1.87 (dt, J = 15.2, 5.3 Hz, 2H),1.75 – 1.69 (m, 2H); 13 C NMR (151 MHz, DMSO-d6) δ 150.07, 147.15, 138.89,133.69, 121.26, 116.49, 114.91, 113.59, 68.94, 64.26, 63.15, 59.35, 57.79,56.57, 55.71, 50.13, 42.52, 40.04, 26.67, 19.82. HRMS (ESI, m / z): [M-Br] + Calcd for C 19 H 32BrNO4: 338.2326; found: 338.23227.

[0108] The characterization data of eugenol quaternary ammonium salt Ⅰ-7 (2M) by NMR hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.92 (d, J = 8.1 Hz, 1H), 6.82 (d, J = 1.3 Hz, 1H), 6.71 (d, J =8.1 Hz, 1H), 5.96 (ddt, J = 16.8, 10.0, 6.8 Hz, 1H), 5.29 (s, 2H), 5.12 –5.03 (m, 2H), 3.99 (t, J = 6.1 Hz, 2H), 3.85 (d, J = 2.5 Hz, 4H), 3.77 (s,3H), 3.49 (dd, J = 10.3, 5.8 Hz, 6H), 3.41 – 3.37 (m, 2H), 3.32 (d, J = 6.7Hz, 2H), 1.85 (dd, J = 15.2, 7.5 Hz, 2H), 1.76 (dd, J = 12.7, 6.2 Hz, 2H), 1.71 – 1.64 (m, 2H), 1.35 – 1.27 (m, 2H), 0.92 (t, J = 7.4 Hz, 3H); 13 C NMR(151 MHz, DMSO-d6) δ 149.97, 147.07, 138.83, 133.54, 121.15, 116.37, 114.67,113.49, 68.65, 61.03, 60.11, 59.81, 56.46, 55.43, 39.97, 26.45, 24.08, 20.04,19.29, 14.33. HRMS (ESI, m / z): [M-Br] + Calcd for C 22 H 38 BrNO4: 380.2795; found:380.27908.

[0109] The characterization data of eugenol quaternary ammonium salt Ⅰ-8 (2N) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1H NMR (400 MHz, DMSO-d6) δ 6.92 (d, J = 8.1 Hz, 1H), 6.81 (s, 1H), 6.70 (dd, J = 8.1 Hz, 1H), 5.96 (ddt, J = 16.8, 10.0, 6.7 Hz, 1H), 5.13 – 5.01 (m, 2H), 4.00 (t, J = 5.9Hz, 2H), 3.77 (s, 3H), 3.41 (s, 2H), 3.35 – 3.28 (m, 4H), 3.08 (s, 6H), 1.84(dd, J = 14.8, 7.5 Hz, 2H), 1.77 (dd, J = 12.2, 5.9 Hz, 2H), 1.66 (s, 2H),1.26 (s, 18H), 0.87 (t, J = 6.7 Hz, 3H); 13 C NMR (126 MHz, DMSO-d6) δ 149.96,147.11, 138.80, 133.51, 121.15, 116.32, 114.65, 113.45, 68.72, 63.79, 63.35,56.43, 50.99, 39.95, 32.23, 29.95, 29.89, 29.79, 29.64, 29.44, 26.74, 26.53,23.02, 22.65, 19.89, 14.83. HRMS (ESI, m / z): [M-Br] + Calcd for C 28 H 50 BrNO2:432.3836; found: 432.38169.

[0110] The characterization data of eugenol quaternary ammonium salt Ⅰ-9 (2O) by H NMR and C NMR are as follows: 1H NMR (600 MHz, DMSO-d6) δ 6.95 (d, J = 8.1 Hz, 1H), 6.83 (s, 1H), 6.71 (d, J = 7.9 Hz, 1H), 6.00 – 5.92 (m, 1H), 5.06 (dd, J = 26.1, 13.2 Hz, 2H), 4.03 (s, 2H), 3.78 (s,3H), 3.41 – 3.36 (m, 2H), 3.32 (d, J = 5.9 Hz, 2H), 3.14 (s, 6H), 2.16 (s,2H), 1.69 (s, 2H), 1.25 (s, 24H), 0.87 (t, J = 5.9 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ 149.97, 147.10, 138.80, 133.53, 121.13, 116.32, 114.66, 113.47,68.70, 63.80, 63.37, 57.50, 56.43, 50.98, 43.00, 39.98, 32.19, 29.96, 29.92,29.85, 29.74, 29.60, 29.40, 26.83, 26.71, 26.51, 24.60, 22.98, 22.60, 19.87,14.80. HRMS (ESI, m / z): [M-Br] + Calcd for C 30 H 54 BrNO2: 460.4149; found:460.41373.

[0111] The characterization data of eugenol quaternary ammonium salt Ⅰ-10 (2P) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1H NMR (400 MHz, DMSO-d6) δ 6.91 (d, J = 8.2 Hz, 1H), 6.81 (d, J = 1.6 Hz, 1H), 6.70 (dd, J =8.1, 1.6 Hz, 1H), 5.95 (ddt, J = 16.8, 10.0, 6.7 Hz, 1H), 5.12 – 5.01 (m,2H), 3.99 (t, J = 5.9 Hz, 2H), 3.77 (s, 3H), 3.40 (s, 2H), 3.34 – 3.28 (m,4H), 3.08 (s, 6H), 1.84 (dd, J = 14.7, 7.6 Hz, 2H), 1.76 (dd, J = 12.2, 5.9Hz, 2H), 1.65 (s, 2H), 1.25 (s, 24H), 0.87 (t, J = 6.7 Hz, 3H); 13 C NMR (151MHz, DMSO-d6) δ 149.54, 146.68, 138.36, 133.09, 120.70, 115.87, 114.23,113.03, 68.28, 63.36, 62.92, 56.25, 55.99, 50.55,39.56,31.77,29.54,29.51,29.50,29.45,29.34,29.19,28.99,26.29,26.08,22.56,22.19,19.44,14.36.HRMS (ESI, m / z): [M-Br] + Calcd for C 32 H 58 BrNO2: 488.4462; found: 488.44426.

[0112] Example 11 to Example 15

[0113] Examples 11 to 15 provide a method for preparing a eugenol quaternary ammonium salt, respectively. The types of brominated eugenol and alkyl tertiary amine ligands used, and the structural formulas of the obtained eugenol quaternary ammonium salts are shown in Table 3 below.

[0114] Table 3 Structural formulas of brominated eugenol, alkyl tertiary amine ligands, and eugenol quaternary ammonium salts in Examples 11 to 15

[0115]

[0116] The characterization data of eugenol quaternary ammonium salt Ⅰ-11 (3L) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.90 (d, J = 8.2 Hz, 1H), 6.80 (s, 1H), 6.69 (d, J = 8.0 Hz, 1H), 5.95 (dq, J = 9.8, 6.8 Hz, 1H), 5.11 – 5.02 (m, 2H), 3.94 (t, J = 6.3 Hz, 2H), 3.87 (s, 4H), 3.75 (s, 3H), 3.59 (t, J = 5.9 Hz, 2H), 3.51 (d, J = 5.1Hz, 2H), 3.48 – 3.43 (m, 2H), 3.30 (d, J = 6.6 Hz, 2H), 3.14 (s, 3H), 2.75(t, J = 5.8 Hz, 2H), 1.77 (td, J = 13.7, 6.8 Hz, 4H), 1.47 – 1.40 (m, 2H); 13 CNMR (151 MHz, DMSO-d6) δ 149.98, 147.38, 138.94, 133.40, 121.26, 116.46,114.54, 113.59, 69.17, 64.21, 63.44, 59.78, 58.40, 56.53, 55.77, 50.05,42.87, 40.04, 29.22, 23.58, 22.41. HRMS (ESI, m / z): [M-Br] + Calcd for C 20 H 34 BrNO4: 352.2482; found: 352.24697.

[0117] The characterization data of eugenol quaternary ammonium salt Ⅰ-12 (3M) by NMR hydrogen spectrum and carbon spectrum are as follows: 1H NMR (600 MHz, DMSO-d6) δ 6.90 (d, J = 8.1 Hz, 1H), 6.80 (s, 1H), 6.69 (d, J = 8.0 Hz, 1H), 5.95 (dq, J = 9.3, 6.8 Hz, 1H), 5.30 (s, 2H), 5.06 (dd, J = 26.4, 13.5 Hz,2H), 3.94 (t, J = 6.1 Hz, 2H), 3.84 (s, 4H), 3.76 (s, 3H), 3.48 (s, 4H), 3.40(dd, J = 15.8, 10.7 Hz, 4H), 3.30 (d, J = 6.5 Hz, 2H), 1.81 – 1.74 (m, 4H), 1.67 (s, 2H), 1.48 – 1.41 (m, 2H), 1.31 (dd, J = 14.4, 7.2 Hz, 2H), 0.93 (t,J = 7.4 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ 149.94, 147.33, 138.85, 133.31,121.17, 116.33, 114.55, 113.53, 69.16, 60.98, 60.20, 60.08, 56.48, 55.46,39.96, 29.13, 24.16, 23.48, 21.95, 20.05, 14.37. HRMS (ESI, m / z): [M-Br] + Calcd for C 23 H 40 BrNO4: 394.2952; found: 394.29414.

[0118] The characterization data of eugenol quaternary ammonium salt Ⅰ-13 (3N) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1H NMR (600 MHz, DMSO-d6) δ 6.96 (dd, J = 10.2, 8.6 Hz, 1H), 6.81 (s, 1H), 6.69 (d, J = 7.9Hz, 1H), 6.00 – 5.90 (m, 1H), 5.05 (dd, J = 26.7, 13.5 Hz, 2H), 4.03 (s, 2H), 3.77 (s, 3H), 3.51 (d, J = 6.7 Hz, 2H), 3.43 – 3.37 (m, 2H), 3.30 (d, J = 6.1Hz, 2H), 3.15 (s, 6H), 2.16 (s, 2H), 1.68 (s, 2H), 1.24 (s, 18H), 0.85 (t, J= 6.0 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ 149.92, 147.31, 138.81, 133.27,121.11, 116.27, 114.44, 113.50, 69.03, 63.84, 63.70, 56.41, 50.83, 49.42,46.53, 39.96, 32.17, 29.94, 29.89, 29.84, 29.73, 29.59, 29.39, 29.10, 26.69,23.51, 22.96, 22.61, 22.38, 14.78, 9.38. HRMS (ESI, m / z): [M-Br] + Calcd for C 29 H 52 BrNO2: 446.3993; found: 446.39756.

[0119] The characterization data of eugenol quaternary ammonium salt Ⅰ-14 (3O) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1H NMR (400 MHz, DMSO-d6) δ 6.91 (d, J = 8.2 Hz, 1H), 6.81 (d, J = 1.5 Hz, 1H), 6.73 – 6.68(m, 1H), 5.97 (ddt, J = 16.8, 10.0, 6.7 Hz, 1H), 5.14 – 5.02 (m, 2H), 3.96 (t, J = 6.3 Hz, 2H), 3.77 (s, 3H), 3.32 (d, J = 6.1 Hz, 4H), 3.06 (s, 6H), 1.84 – 1.72 (m, 4H), 1.67 (s, 2H), 1.46 (dt, J = 14.6, 7.4 Hz, 2H), 1.27 (s,24H), 0.88 (t, J = 6.7 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ 149.93, 147.33,138.82, 133.27, 121.13, 116.27, 114.44, 113.50, 69.07, 63.84, 63.70, 56.43,50.85, HRMS (ESI, m / z): [M-Br] + Calcd for C 31 H 56 BrNO2: 474.4306; found: 474.42958.

[0120] The characterization data of eugenol quaternary ammonium salt Ⅰ-15 (3P) by NMR hydrogen spectrum and carbon spectrum are as follows: 1H NMR (400 MHz, DMSO-d6) δ 6.90 (d, J = 8.2 Hz, 1H), 6.80 (d, J = 1.6 Hz, 1H), 6.70 (dd, J =8.1, 1.5 Hz, 1H), 5.96 (ddt, J = 16.8, 10.0, 6.7 Hz, 1H), 5.13 – 5.02 (m,2H), 3.96 (t, J = 6.3 Hz, 2H), 3.76 (s, 3H), 3.31 (d, J = 6.6 Hz, 4H), 3.13(q, J = 7.3 Hz, 2H), 3.05 (s, 6H), 1.78 (dt, J = 13.2, 6.5 Hz, 4H), 1.66 (s,2H), 1.50 – 1.36 (m, 4H), 1.29 – 1.21 (m, 26H), 0.88 (t, J = 6.7 Hz, 3H); 13 CNMR (151 MHz, DMSO-d6) δ 149.50, 146.88, 138.42, 132.89, 120.72, 115.91,114.02, 113.09, 68.61, 63.46, 63.32, 56.00, 50.43, 46.15,39.54,31.76,29.48,29.40,29.29,29.17,28.96,28.68,26.27,23.10,22.55,22.19,21.96,14.40,9.01. m / z): [M-Br] + Calcd for C 33 H 60 BrNO2: 502.4619; found:502.45983.

[0121] Example 16 to Example 20

[0122] Examples 16 to 20 provide a method for preparing a eugenol quaternary ammonium salt, respectively. The types of brominated eugenol and alkyl tertiary amine ligands used, and the structural formulas of the obtained eugenol quaternary ammonium salts are shown in Table 4 below.

[0123] Table 4 Structural formulas of brominated eugenol, alkyl tertiary amine ligands, and eugenol quaternary ammonium salts in Examples 16 to 20

[0124]

[0125] The characterization data of eugenol quaternary ammonium salt Ⅰ-16 (4L) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1 H NMR (600 MHz, DMSO-d6) δ 6.89 (d, J = 8.1 Hz, 1H), 6.80 (s, 1H), 6.69 (d, J = 8.0 Hz, 1H), 5.96 (ddt, J = 13.2, 9.5, 6.7 Hz, 1H), 5.07 (dd, J = 26.2, 13.5 Hz, 2H), 3.92(t, J = 5.5 Hz, 2H), 3.86 (s, 4H), 3.76 (s, 3H), 3.60 (d, J = 5.3 Hz, 2H), 3.50 (s, 2H), 3.46 – 3.40 (m, 2H), 3.31 (d, J = 6.1 Hz, 2H), 3.14 (s, 3H),2.78 (s, 1H), 2.48 (s, 1H), 1.74 (d, J = 5.7 Hz, 4H), 1.51 – 1.44 (m, 2H),1.35 (d, J = 6.6 Hz, 2H); 13 C NMR (151 MHz, DMSO-d6) δ 149.88, 147.37, 138.91,133.19, 121.17, 116.40, 114.27, 113.48, 69.07, 64.10, 63.31, 59.65, 58.21,56.43, 55.68, 49.96, 42.73, 40.00, 29.51, 26.46, 26.00, 22.50. HRMS (ESI, m / z): [M-Br] + Calcd for C 21 H 36 BrNO4: 366.2639; found: 366.26305.

[0126] The characterization data of eugenol quaternary ammonium salt Ⅰ-17 (4M) by NMR hydrogen spectrum and carbon spectrum are as follows: 1H NMR (600 MHz, DMSO-d6) δ 6.89 (d, J = 8.1 Hz, 1H), 6.80 (s, 1H), 6.70 (d, J = 8.0 Hz, 1H), 5.96 (dq, J = 9.8, 6.8 Hz, 1H), 5.29 (s, 2H), 5.07 (dd, J = 26.1, 13.5 Hz,2H), 3.93 (t, J = 6.2 Hz, 2H), 3.83 (s, 4H), 3.76 (s, 3H), 3.47 (s, 4H), 3.40– 3.36 (m, 4H), 3.31 (d, J = 6.4 Hz, 2H), 1.73 (dd, J = 14.2, 6.8 Hz, 4H), 1.53 – 1.44 (m, 2H), 1.33 (dt, J = 21.5, 7.0 Hz, 6H), 0.95 – 0.92 (m, 3H); 13 CNMR (151 MHz, DMSO-d6) δ 149.89, 147.37, 138.90, 133.21, 121.16, 116.38,114.30, 113.49, 69.09, 60.92, 60.17, 59.98, 56.42, 55.46, 39.99, 29.53,26.42, 25.97, 24.14, 22.10, 20.41, 20.07. HRMS (ESI, m / z): [M-Br] + Calcd for C 24 H 42 BrNO4: 408.3108; found: 408.30969.

[0127] The characterization data of eugenol quaternary ammonium salt Ⅰ-18 (4N) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1H NMR (600 MHz, DMSO-d6) δ 6.89 (d, J = 8.1 Hz, 1H), 6.81 (s, 1H), 6.70 (d, J = 8.0 Hz, 1H), 5.97 (dq, J = 9.9, 6.8 Hz, 1H), 5.08 (dd, J = 25.7, 13.5 Hz, 2H), 3.94 (t, J= 6.3 Hz, 2H), 3.76 (s, 3H), 3.32 (d, J = 6.4 Hz, 6H), 3.05 (s, 6H), 1.78 –1.73 (m, 2H), 1.70 (d, J = 5.1 Hz, 4H), 1.53 – 1.47 (m, 2H), 1.38 – 1.35 (m,2H), 1.28 (s, 18H), 0.88 (t, J = 6.8 Hz, 3H); 13 C NMR (151 MHz, DMSO-d6) δ149.93, 147.37, 138.85, 133.23, 121.15, 116.33, 114.38, 113.55, 69.12, 63.84,63.78, 56.43, 50.85, 44.53, 39.96, 32.18, 29.90, 29.82, 29.70, 29.59, 29.46,29.36, 26.67, 26.41, 25.95, 22.97, 22.60, 22.57, 22.50, 14.82. HRMS (ESI, m / z): [M-Br] + Calcd for C 30 H 54 BrNO2: 460.4149; found: 460.41369.

[0128] The characterization data of eugenol quaternary ammonium salt Ⅰ-19 (4O) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 1H NMR (400 MHz, DMSO-d6) δ 6.86 (d, J = 8.2 Hz, 1H), 6.78 (d, J = 1.5 Hz, 1H), 6.69 – 6.64(m, 1H), 5.94 (ddt, J = 16.8, 10.0, 6.7 Hz, 1H), 5.11 – 4.99 (m, 2H), 3.91(t, J = 6.4 Hz, 2H), 3.74 (s, 3H), 3.29 (d, J = 6.8 Hz, 4H), 3.04 (s, 6H),1.70 (ddd, J = 18.7, 14.7, 7.0 Hz, 6H), 1.47 (dt, J = 14.8, 7.4 Hz, 2H), 1.35(dd, J = 12.8, 5.7 Hz, 2H), 1.24 (s, 24H), 0.85 (t, J = 6.7 Hz, 3H); 13 C NMR(151 MHz, DMSO-d6) δ 149.93, 147.38, 138.84, 133.21, 121.14, 116.30, 114.36,113.53, 69.12, 63.82, 63.75, 56.42, 50.86, 39.98,32.20,29.97,29.93,29.85,29.74,29.61,29.47,29.40,26.69,26.42,25.96,22.99,22.62,22.58,14.81.HRMS (ESI, m / z): [M-Br] + Calcd for C 32 H 58 BrNO2: 488.4462; found: 488.44509.

[0129] The characterization data of eugenol quaternary ammonium salt Ⅰ-20 (4P) by nuclear magnetic hydrogen spectrum and carbon spectrum are as follows: 11H NMR (400 MHz, CDCl3) δ 6.80 (d, J = 8.6 Hz, 1H), 6.70 (d, J = 5.8 Hz, 2H), 5.95 (ddt, J = 16.8, 10.0, 6.7 Hz, 1H), 5.07 (dd, J = 13.1, 7.5 Hz, 2H), 3.98 (t, J = 6.4 Hz, 2H), 3.84 (s, 3H), 3.58 – 3.47 (m, 4H), 3.41 (s, 6H), 3.33 (d, J = 6.7 Hz, 2H), 1.87 – 1.79 (m, 2H), 1.72 (dd, J = 15.5, 7.6 Hz, 4H), 1.61 – 1.52 (m, 2H), 1.51 – 1.43 (m, 2H), 1.25 (s, 26H), 0.88 (t, J = 6.6 Hz, 3H); 13 13C NMR(151 MHz, DMSO-d6) δ 149.51, 146.96, 138.43, 132.81, 120.72, 115.90, 113.95, 113.13, 68.69, 63.42, 63.36, 56.00, 50.44, 39.54, 31.76, 29.52, 29.48, 29.41, 29.28, 29.17, 29.04, 28.95, 26.26, 26.00, 25.54, 22.55, 22.16, 22.14, 14.39. HRMS (ESI, m / z): [M-Br] + Calcd for C 34 H 62 BrNO2: 516.4775; found: 516.47622.

[0130] Performance testing

[0131] Commercially available didecyldimethylammonium chloride (DDAC, CAS: 7173-51-5) and dodecyldimethylbenzylammonium chloride (DDBAC, CAS: 139-07-1) were used as positive controls to perform a preliminary screening test on the eugenol quaternary ammonium salts prepared in Examples 1 to 20 of the present invention for inhibiting wood decay fungi. The mycelium growth rate method was used to determine the inhibitory activity against the test fungi, comprising: preparing the eugenol quaternary ammonium salts prepared in Examples 1 to 20 into a 20 mg / mL stock solution, and pipetting 400 μL of the stock solution into 80 mL of sterilized PDA culture medium. A 100 μg / mL drug-containing culture medium was prepared, a culture medium containing an equal amount of distilled water was used as a blank control, and a culture medium containing an equal amount of DDAC and DDBAC was used as a positive control; the culture medium was poured into a culture dish and cooled, and then a bacterial cake with a diameter of 8 mm was taken from the outer edge of the colony after 5 days of subculture using a sterile punch and inoculated on the culture medium. Each treatment was repeated 3 times and cultured in a constant temperature incubator at 28°C for 5-7 days. When the mycelium in the control group culture medium was full of 3 / 4, the colony growth diameter was measured by the cross method and the mycelium growth inhibition rate was calculated according to the following formula as shown in Table 5.

[0132]

[0133] Table 5 Inhibition rate of mycelial growth of wood decay fungi at 100 μg / mL

[0134]

[0135] As can be seen from Table 5, most of the compounds prepared in the present invention exhibit good in vitro antibacterial activity against two wood decay fungi, and when the alkyl tertiary amine ligand is N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine and N,N-dimethylhexadecylamine, the inhibitory effect on wood decay fungi is better than that of the compounds when the alkyl ligand ligand is N-methyldiethanolamine and N-butyldiethanolamine.

[0136] Among them, when the compound concentration was 100 μg / mL, the inhibition rates of 11 compounds (1N, 2N, 3N, 4N, 1O, 2O, 3O, 4O, 2P, 3P, 4P) against Coriolus versicolor exceeded those of the commercial monoquaternary ammonium preservative DDAC, and the inhibition rate of one compound (3N) exceeded that of the commercial diquaternary ammonium preservative DDBAC. The inhibition rates of two compounds (3O and 4O) against Glehnia littoralis were close to those of the commercial monoquaternary ammonium preservatives DDAC and DDBAC. This indicates that eugenol quaternary ammonium salts obtained by substitution with N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, and N,N-dimethylhexadecylamine have the potential to become commercial preservatives.

[0137] According to the initial screening activity results in Table 5, the compounds with higher inhibition rates were selected to determine the EC values ​​of wood decay fungi. 50The compound stock solution was diluted with sterile water by the two-fold dilution method. 400 μL of the stock solution was accurately transferred to 80 mL of sterilized PDA medium with a pipette. After thorough mixing, the mixture was poured into a 90 mm disposable sterile culture dish to prepare a series of drug-containing culture media. Sterile water was used as a blank control and DDBAC as a positive control. Each treatment was repeated 3 times. When the blank control mycelium grew to 3 / 4, the mycelium growth diameter was measured by the cross-cross method, and the inhibition rate of different concentrations of compounds on different strains was calculated according to the mycelium growth inhibition rate formula. Using SPASS (PASW Statistics 18) software, with the logarithm of the concentration as the horizontal axis and the inhibition rate as the vertical axis, linear fitting was performed to obtain the toxicity regression equation and correlation coefficient R 2 Value, EC 50 Value and EC 90 The data were compared with Duncan's multiple comparison test, as shown in Tables 6 and 7 below.

[0138] Table 6 Linear fitting data of the toxicity of the compounds obtained in the initial screening against Coriolus versicolor

[0139]

[0140] Table 7 Linear fitting data of the toxicity of the compounds obtained in the initial screening against Pseudomonas aeruginosa

[0141]

[0142] As can be seen from Table 6, the EC values ​​of the five compounds are 50 The value is better than the commercial preservative monoquaternary ammonium salt DDBAC (EC 50 is 10.21 μg / mL), respectively for compounds 1N, 1O, 2N, 3N and 4N, EC 50 In the range of 6.76~9.76μg / mL, three compounds (1N, 2N and 3N) outperformed the commercial preservative diquaternary ammonium salt DDAC (EC 50 As shown in Table 7, compound 1N still has the strongest antibacterial activity, and its EC 50 The value was 2.11 μg / mL, which was better than the commercial preservative monoquaternary ammonium salt DDBAC (EC 50 =3.33μg / mL) and diquaternary ammonium salt DDAC (EC 50 =5.59 μg / mL), followed by compound 3N (EC 50 = 3.09 μg / mL), followed by compound 2O (EC 50 =4.10 μg / mL).

[0143] While the embodiments of the present invention have been described in detail above, it will be apparent to those skilled in the art that various modifications and variations of these embodiments are possible. However, it should be understood that such modifications and variations are within the scope and spirit of the present invention as set forth in the claims. Furthermore, the invention described herein is susceptible to other embodiments and may be practiced or implemented in a variety of ways.

Claims

1. An application of eugenol quaternary ammonium salt in wood preservation, characterized in that, The structure of the eugenol quaternary ammonium salt is one of the following structural formulas: ； ； ； ； ； Wherein, v is any integer from 3 to 6.

2. The use according to claim 1, characterized in that include: Under alkaline conditions, dibromoalkane is introduced into eugenol for nucleophilic substitution to generate brominated eugenol, and an alkyl tertiary amine ligand is introduced to perform quaternization reaction to form a salt to obtain eugenol quaternary ammonium salt.

3. The use according to claim 2, characterized in that The following steps are involved: The dibromoalkane and eugenol are reacted under alkaline conditions to generate bromoeugenol; the bromoeugenol is reacted with an alkyl tertiary amine ligand to form a salt to obtain eugenol quaternary ammonium salt.

4. The use according to claim 2 or 3, characterized in that The reaction is carried out under alkaline conditions at 60° C.-80° C.; and / or, the reaction is carried out under alkaline conditions for 36 h-60 h; and / or, the molar ratio of the eugenol to the dibromoalkane is 1:(2-10); and / or, after the reaction under alkaline conditions, the eugenol is separated and impurities are removed, and the bromoeugenol is purified by rotary evaporation and column chromatography to obtain brominated eugenol.

5. The use according to claim 2 or 3, characterized in that The bromoeugenol and the alkyl tertiary amine ligand are reacted at 20° C.-30° C.; and / or, the bromoeugenol and the alkyl tertiary amine ligand are reacted for 1 hour-24 hours; and / or, the molar ratio of the bromoeugenol to the alkyl tertiary amine ligand is 1:(1-5); and / or, after the quaternization reaction, the salt is formed and the quaternary ammonium salt is purified by rotary evaporation and column chromatography to obtain the eugenol quaternary ammonium salt.

6. The use according to claim 2, characterized in that The reaction formula for introducing dibromoalkane into eugenol for nucleophilic substitution to generate bromoeugenol is: ； Wherein, v is any integer from 3 to 6.

7. The use according to claim 6, characterized in that The reaction formula for preparing eugenol quaternary ammonium salt by introducing alkyl tertiary amine into the quaternization reaction is: ； Wherein, the R group includes R-1 or R-2; ， ； Wherein, m is 0 or 3, and n is 11, 13 or 15.

8. The use according to claim 2, characterized in that The dibromoalkane includes one of 1,3-dibromopropane, 1,4-dibromobutane, 1,5-dibromopentane, and 1,6-dibromohexane; and / or the alkyl tertiary amine ligand includes one of N-methyldiethanolamine, N-butyldiethanolamine, N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, and N,N-dimethylhexadecylamine.

Images