A N 1 ,N 1 ,N 2 ,N 2 - Tetra(4-fluorobenzyl)cyclohexane-1,2-diamine and methods of preparation and use

Abstract

The application belongs to the technical field of fertilizer synergist, and particularly relates to N 1 ,N 1 ,N 2 ,N 2 -Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine and preparation method and application. The preparation method is as follows: 1,2-cyclohexanediamine and 4-fluorobenzyl bromide are used as raw materials, water is used as a reaction solvent, sodium hydroxide is used as a catalyst, the reaction system is heated under reflux, and a target compound is obtained. The target product is used as a fertilizer synergist, and results show that the fertilizer synergist can significantly increase the root length of garlic and has obvious growth-promoting effect; field test of spinach shows that the novel fertilizer synergist can significantly increase the yield of spinach. In the synthesis process, there are few by-products, the solvent water can be recycled, the fertilizer synergist is suitable for being added to the fertilizer for use, and has the prospect of large-scale production and application.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of fertilizer synergist, and particularly relates to a kind of N 1 ,N 1 ,N 2 ,N 2 -Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine and preparation method and application. BACKGROUND

[0002] Fertilizer synergist can significantly improve the utilization rate of fertilizer, increase the yield of crops, and promote the growth of crop root system, which includes natural fertilizer synergist and synthetic fertilizer synergist. Unlike natural fertilizer synergist with low content in plants and high extraction cost, synthetic fertilizer synergist can be produced on a large scale and widely used in agricultural field to improve and guarantee the yield and quality of harvested crops. Fertilizer synergist is widely used in modern agriculture, horticulture and grape cultivation. New fertilizer synergist for promoting root growth can actively regulate plant development process in cultivated plants, such as accelerating or delaying seed germination, dormancy breaking of woody perennial plants. The benefits include promoting crop management, improving and guaranteeing the yield and quality of harvested products, and improving their storage and shelf life. However, the types of fertilizer synergist are relatively single, and the cost is high. Most of the fertilizer synergist is to control the slow release of nitrogen, thereby improving the utilization rate of fertilizer, and there are few studies on new fertilizer synergist for promoting root growth and increasing crop yield. SUMMARY

[0003] To solve the above technical problems, the application provides a kind of N 1 ,N 1 ,N 2 ,N 2 -Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine and preparation method and application. Compound N 1 ,N 1 ,N 2 ,N 2 -Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine can significantly promote the growth of plant root system and increase the net weight of plant when used as fertilizer synergist, and has no pollution to the environment. The application further increases the types of fertilizer synergist and improves the utilization rate of fertilizer.

[0004] The application is realized by providing a kind of N 1 ,N 1 ,N 2 ,N 2 -Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine, the molecular formula is C 34 H 34 N2F4, the structural formula is:

[0005] .

[0006] The preparation method of the above-mentioned N 1 ,N 1 ,N 2 ,N 2 The preparation method of tetra (4-fluorobenzyl) cyclohexane-1,2-diamine adopts 1,2-cyclohexanediamine and 4-fluorobenzyl bromide as raw materials, water as a reaction solvent, sodium hydroxide as a catalyst, and the reaction system is heated under reflux to obtain the target compound N 1 ,N 1 ,N 2 ,N 2 Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine.

[0007] The preparation method is simple, the solvent can be recycled and reused multiple times, is green and environmentally friendly, has high yield (> 87%), and the product structure is clear; the solvent water can be recycled and reused multiple times, effectively reducing wastewater discharge in the production process, and providing a new research direction for high-quality green development of agriculture.

[0008] According to the preferred embodiment of the present application, 1,2-cyclohexanediamine and 4-fluorobenzyl bromide are put into a water solvent containing sodium hydroxide, heated and reacted, after the reaction is completed, the reaction system is cooled to room temperature, filtered, the solid is recrystallized with methanol, then filtered, and dried to obtain the N 1 ,N 1 ,N 2 ,N 2 Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine.

[0009] Preferably, the reaction is heated at 90-100°C for 4-10h, and the reaction is carried out under reflux.

[0010] Preferably, the molar ratio of 1,2-cyclohexanediamine to 4-fluorobenzyl bromide is 1:2-5, preferably 1:4. Under the above-mentioned molar ratio and reaction conditions, the generation of by-products can be reduced, and the yield of the target product can be improved.

[0011] Preferably, the amount of water solvent added accounts for 40-50% of the total mass of the reaction system, and the amount of catalyst sodium hydroxide added accounts for 1-10% of the total mass of the reaction system.

[0012] Preferably, the drying temperature is 80-105°C, and the drying time is 0.5-1.5h.

[0013] The application of the above-mentioned N 1 ,N 1 ,N 2 ,N 2 Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine is used as a fertilizer synergist.

[0014] Preferably, the fertilizer synergist N 1 ,N 1 ,N 2 ,N 2 - Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine is added to compound fertilizer or complex fertilizer for use.

[0015] Compared with the prior art, the present application has the advantages of:

[0016] The compound N 1 ,N 1 ,N 2 ,N 2 - Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine can be used as a fertilizer synergist, which can significantly promote the growth of plants and increase the net weight of plants. When used as a fertilizer synergist, N 1 ,N 1 ,N 2 ,N 2 - Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine is added to compound fertilizer or complex fertilizer for use, which promotes the growth of crop roots, has good effect on improving crop yield, and has little environmental pollution.

[0017] The compound N 1 ,N 1 ,N 2 ,N 2 - Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine has less by-products in the synthesis process, the reaction solvent water can be recycled and reused multiple times, is green and environmentally friendly, has high yield (> 87%) and stable product performance, and has the prospect of large-scale production and related product application. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 The single crystal structure diagram of the target product prepared in Example 1. DETAILED DESCRIPTION

[0019] In order to better explain the present application, so as to be understood, the present application is described in detail in combination with the drawings and through specific embodiments.

[0020] Example 1

[0021] This embodiment includes the synthesis and structural characterization of the target compound.

[0022] 20.0 g (175 mmol) of 1,2-cyclohexanediamine and 132.43 g (700 mmol) of 4-fluorobenzyl bromide were weighed and placed in a 500 mL round-bottom flask. Then, 152 mL of water was added, followed by 16 g of sodium hydroxide catalyst. The mixture was refluxed at 100 °C for 8 h. After the reaction was complete, the mixture was cooled and filtered, then dried at 105 °C for 1 h to obtain 85.5 g of a white powder, with a yield of 89.3%. The reaction process is shown below:

[0023]

[0024] Structural characterization:

[0025] The above N 1 N 1 N 2 N 2 Structural characterization of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine: Diffraction intensity data of the single crystal were collected using graphite monochromatic Mo Kα (λ = 0.71073 Å) radiation as the diffraction source on a Bruker D8 X-ray diffractometer. N2O3 was obtained from the colorless bulk crystal prepared in Example 1. 1 N 1 N 2 N 2 Data obtained from the SC-XRD of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, and further obtained as shown in the appendix. Figure 1 The structure shown, N 1 N 1 N 2 N 2 The molecular formula of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine is C2 34 H 34 N2F4, crystal form belongs to the monoclinic system, space group [missing information]. C2 / c Specific single-crystal data are shown in Table 1.

[0026] Table 1: N 1 N 1 N 2 N 2 Key crystallographic data of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine

[0027] Molecule of the compound Formula ]] C 34 H 34 N2F4]]> Molecular weight of the compound 546.63 Test temperature (K) of the compound 296 Crystal system of the compound Monoclinic Space group of the compound / Å 17.944(5) / Å 11.167(3) / Å 15.150(4) / ° 90 / ° 106.788(8) / ° 90 Volume of compound (A 3 )]]> 2906.4(13) Theoretical density (g cm -3 )]]> 1.249 Linear absorption coefficient of cells (mm -1 )]]> 0.090 Number of electrons in the unit cell 1152.0 Standard error of the mean of equivalent points 0.0607 S value for observable diffraction points 1.016 R1 value for observable diffraction points 0.0726 R2 value for all diffraction points 0.2559 .

[0028] Example 2

[0029] Take 20.0 g (175 mmol) 1,2-cyclohexanediamine, and 132.43 g (700 mmol) 4- fluorobenzyl bromide into a 500 mL round-bottom flask, then add 152 mL solvent water, add 16 g catalyst sodium hydroxide, reflux at 100°C for 5h, after the reaction is completed, cool and filter, dry at 105°C for 1h, to get white powder 83.5g, yield 87.2%.

[0030] Example 3

[0031] Take 20.0 g (175 mmol) 1,2-cyclohexanediamine, and 132.43 g (700 mmol) 4- fluorobenzyl bromide into a 500 mL round-bottom flask, then add 152 mL solvent water, add 16 g catalyst sodium hydroxide, reflux at 100°C for 5h, after the reaction is completed, cool and filter, dry at 105°C for 1h, to get white powder 83.5g, yield 87.2%.

[0032] Example 4

[0033] Take 20.0 g (175 mmol) 1,2-cyclohexanediamine, and 132.43 g (700 mmol) 4- fluorobenzyl bromide into a 500 mL round-bottom flask, then add 152 mL solvent water, add 16 g catalyst sodium hydroxide, reflux at 100°C for 5h, after the reaction is completed, cool and filter, dry at 105°C for 1h, to get white powder 83.5g, yield 87.2%.

[0034] Example 5

[0035] Take 20.0 g (175 mmol) 1,2-cyclohexanediamine, and 132.43 g (700 mmol) 4- fluorobenzyl bromide into a 500 mL round-bottom flask, then add 152 mL solvent water, add 16 g catalyst sodium hydroxide, reflux at 100°C for 5h, after the reaction is completed, cool and filter, dry at 105°C for 1h, to get white powder 83.5g, yield 87.2%.

[0036] Example 6

[0037] Take 20.0 g (175 mmol) 1,2-cyclohexanediamine, and 132.43 g (700 mmol) 4- fluorobenzyl bromide into a 500 mL round-bottom flask, then add 152 mL solvent water, add 16 g catalyst sodium hydroxide, reflux at 100°C for 5h, after the reaction is completed, cool and filter, dry at 105°C for 1h, to get white powder 83.5g, yield 87.2%.

[0038] Example 7

[0039] Take 20.0 g (175 mmol) 1,2-cyclohexanediamine, and 132.43 g (700 mmol) 4- fluorobenzyl bromide into a 500 mL round-bottom flask, then add 152 mL of solvent water, add 10 g of catalyst sodium hydroxide, reflux at 90°C for 10 h, after the reaction is completed, filter and dry at 105°C for 1.5 h to obtain 84.1 g of white powder with a yield of 87.8%.

[0040] Example 8

[0041] 1, Garlic seedling growth promotion test: Select healthy and full garlic heads, gently peel off the outer dry skin, separate the garlic cloves, and ensure that each clove has an intact bulb disc. Place the treated garlic cloves with the bud point facing up in the container, leaving a gap of 1-2 cm between the garlic cloves, add water, and apply N 1 ,N 1 ,N 2 ,N 2 - Four (4-fluorobenzyl) cyclohexane-1,2-diamine sample, use water level to just touch the bottom of the garlic clove, observe root length and seedling length data for 7 days. Experimental results analysis: at low concentration, the growth regulator N 1 ,N 1 ,N 2 ,N 2 - Four (4-fluorobenzyl) cyclohexane-1,2-diamine significantly promotes the growth of garlic roots, with a concentration of 5 mg / L, an increase of 0.90 cm in root length compared to the control, an increase of 25.27%, an increase of 2.74 cm in seedling length compared to the control, an increase of 15.65%, but when the concentration is too large, it shows an inhibitory effect, therefore, the amount of addition in fertilizer needs to be controlled.

[0042] Table 2: Data statistics of garlic growth promotion test results at different concentrations

[0043] Product test concentration 1 mg / L 3 mg / L 5 mg / L 10 mg / L CK Root length (cm) 3.74 4.35 4.42 3.2 3.52 Seedling length (cm) 17.64 19.56 20.24 15.30 17.50

[0044] 2, Spinach field test: three treatments were set, treatment 1: conventional fertilization, treatment 2: conventional fertilization + growth regulator N 1 ,N 1 ,N 2 ,N 2 - Four (4-fluorobenzyl) cyclohexane-1,2-diamine, treatment 3: blank control without fertilization. Test method: treatment 1, 2, 30 kg of compound fertilizer (15-15-15) per mu, treatment 3 without fertilization. Sow 1.5 kg per mu, row spacing 15 cm, water after sowing, continue to water every 20 days, apply 20 kg of fertilizer (26-0-4) per mu, and at the same time, treatment 2 applies growth regulator N 1 ,N 1 ,N 2 ,N2 - Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine 10 g / 5L, treatment 3, 5L of water is used to flush the substrate 3 times during the growth period of the disease and pest control, a total of 1.5 months of time Field harvest, test the effects of different treatments on the biological characteristics of spinach at the end of the experiment as shown in Table 3.

[0045] Table 3: Fresh weight data statistics of single plant of different treatments

[0046]

[0047] Result analysis: comparing the single plants of different treatments of spinach, analysis shows that the average fresh weight of single plant of treatment 2 is the highest, which is 21.65 g. The average fresh weight of single plant of treatment 2 is increased by 1.74 g compared with treatment 1, and the weight gain rate is 8.74%; the average weight gain of single plant of treatment 2 is 2.58 g compared with treatment 3, and the weight gain rate is 13.52%. In summary, the novel fertilizer synergist N 1 ,N 1 ,N 2 ,N 2 Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine can be used as a fertilizer synergist, and the cost of flushing is 10 g / acre, and the addition amount of compound fertilizer or compound fertilizer is 1-2 Kg / t.

[0048] Therefore, it can be concluded that the N 1 ,N 1 ,N 2 ,N 2 Tetra (4-fluorobenzyl) cyclohexane-1,2-diamine can be used as a fertilizer synergist, and the cost of flushing is 10 g / acre, and the addition amount of compound fertilizer or compound fertilizer is 1-2 Kg / t.

[0049] Finally, it should be pointed out that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present application.

Claims

1. A N 1 ,N 1 ,N 2 ,N 2 - tetra(4-fluorobenzyl)cyclohexane-1,2-diamine characterized in that, The molecular formula of the compound is C 34 H 34 N2F4, the structural formula of which is 。 2. The N of claim 1 1 ,N 1 ,N 2 ,N 2 - Process for the preparation of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, characterized in that, The 1,2-cyclohexanediamine and 4-fluorobenzyl bromide are used as raw materials, water is used as a reaction solvent, sodium hydroxide is used as a catalyst, the reaction system is heated to reflux, and a target compound N 1 ,N 1 ,N 2 ,N 2 - tetra (4-fluorobenzyl) cyclohexane-1,2-diamine is obtained.

3. The N of claim 2 1 ,N 1 ,N 2 ,N 2 - Process for the preparation of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, characterized in that, Specifically, 1,2-cyclohexanediamine and 4-fluorobenzyl bromide are put into an aqueous solvent containing sodium hydroxide, heated for reaction, after the reaction is completed, the reaction system is cooled to room temperature, filtered, the solid is recrystallized with methanol, then filtered, and dried to obtain the N 1 ,N 1 ,N 2 ,N 2 - Tetra(4-fluorobenzyl)cyclohexane-1,2-diamine.

4. The N of claim 3 1 ,N 1 ,N 2 ,N 2 - Process for the preparation of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, characterized in that, The reaction is heated at 90-100 DEG C for 4-10 h, and is carried out under reflux.

5. The N of claim 3 wherein the N is 1 1 2 2 - Process for the preparation of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, characterized in that, The molar ratio of 1,2-cyclohexanediamine to 4-fluorobenzyl bromide is 1:2-5. ​​​ 6. The N of claim 3 wherein the N is 1 ,N 1 ,N 2 ,N 2 - Process for the preparation of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, characterized in that, The water solvent is added in an amount of 40-50% of the total mass of the reaction system, and the catalyst sodium hydroxide is added in an amount of 1-10% of the total mass of the reaction system.

7. The N of claim 3 wherein the N is 1 ,N 1 ,N 2 ,N 2 - Process for the preparation of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, characterized in that, The drying temperature is 80-105 DEG C, and the drying time is 0.5-1.5 h.

8. The N of claim 1 1 ,N 1 ,N 2 ,N 2 - Use of tetra(4-fluorobenzyl)cyclohexane-1,2-diamine, characterized in that, As a fertilizer synergist.

9. Use according to claim 8, characterized in that, Fertilizer synergist N 1 ,N 1 ,N 2 ,N 2 - Tetra(4-fluorobenzyl)cyclohexane-1,2-diamine is added to compound fertilizers for use.

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