CN115043737B - Tetrahydrolinalool secondary amine compound, preparation method and weeding application thereof - Google Patents

Tetrahydrolinalool secondary amine compound, preparation method and weeding application thereof Download PDF

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CN115043737B
CN115043737B CN202210657090.6A CN202210657090A CN115043737B CN 115043737 B CN115043737 B CN 115043737B CN 202210657090 A CN202210657090 A CN 202210657090A CN 115043737 B CN115043737 B CN 115043737B
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tetrahydrolinalool
secondary amine
reaction
aldehyde
amine
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CN115043737A (en
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赵振东
张红梅
王婧
陈玉湘
徐士超
卢言菊
古研
毕良武
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Institute of Chemical Industry of Forest Products of CAF
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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Abstract

The invention discloses a tetrahydrolinalyl secondary amine compound, a preparation method thereof and weeding application. The method takes tetrahydrolinalool amine and aldehyde as raw materials, carries out condensation reaction in a polar organic solvent at 0-100 ℃, reduces the temperature of a reaction solution to minus 20-60 ℃ after the raw materials fully react, inputs a reducing agent for reaction for 1-24 hours in batches, and obtains tetrahydrolinalool secondary amine compounds through distilled water quenching, dichloromethane extraction, anhydrous sodium sulfate drying, filtration and reduced pressure distillation after the reaction is finished, and the target product pure product is obtained through recrystallization or silica gel column chromatography. And (3) measuring the growth inhibition condition of ryegrass roots and stems under the culture of tetrahydrolinalool secondary amine compounds with different concentrations by adopting a culture dish seed germination method, and evaluating the weeding activity of the ryegrass roots and stems. The method has the advantages of simple process, mild condition, high speed, high yield and wide substrate applicability, and the product has good inhibition effect on the growth of the roots and stems of ryegrass.

Description

Tetrahydrolinalool secondary amine compound, preparation method and weeding application thereof
Technical field:
the invention relates to a tetrahydrolinalool secondary amine compound, a preparation method and weeding application thereof, in particular to a tetrahydrolinalool secondary amine compound which is prepared by directly reducing hydride without separation and purification after reaction of tetrahydrolinalool amine and aldehyde in a polar organic solvent, drying by anhydrous sodium sulfate, filtering and distilling under reduced pressure, and is used as a weeding active ingredient of ryegrass and the like.
Background
Weeds not only compete with crops for water and sunlight, but also bring about plant diseases and insect pests, so that the quality and yield of grains are reduced. For a long time, the application of chemical synthetic herbicide is the most main weeding mode in the current agricultural production, but the long-term massive use of chemical herbicide can generate the influence of environmental pollution, biological toxicity, ecological damage and the like, and can easily cause the resistance of weeds, so that a larger amount of herbicide needs to be applied. Therefore, the development of green and environment-friendly high-performance herbicides provides an effective way for solving the problems, and is one of the development directions of future herbicides.
The plant-derived pesticide is a pesticide with active ingredients derived from plant bodies, is usually prepared by taking plant extracts as raw materials, is used for preventing and controlling agricultural pests, has the advantages of rich sources, high efficiency, low toxicity and biodegradability, and is one of the most widely studied novel environment-friendly pesticides in recent years. Many natural essential oils such as turpentine, perillaldehyde, carvacrol, thymol and the like have good herbicidal activity. Turpentine derived pairsAlkane (1) or p->The alkene (2) skeleton has good environmental compatibility and biological activity, is valued in the field of plant source herbicide development and research, and has good prospect. In 1983, 1, 4-cineole was used as precursor compound to synthesize oxa-ring p ∈>The alkyl derivative cycloheptyl ether (3) is one of the plant source herbicides with the best commercial application effect at present, is used for preventing and killing gramineous weeds in paddy fields, and has the advantages of wide application period and small dosage (1-2 g a.i/mu). The cellobione is a compound separated from melaleuca alternifolia plants, a series of herbicides such as sulcotrione (4), mesotrione, cyclosulfamlone and the like are developed by using the cellobione as a lead compound by a Jie Li Kangnong chemical company (prior Zhengda company) in 1993 and are used for preventing and controlling most broadleaf weeds and partial gramineous weeds in corn fields.
Early research results showed that 3-pair derived from turpentineAlkene-1-amine schiff base and secondary amine derivatives, cis-1, 8-p ∈ ->The alkanediamine schiff base and the secondary amine derivative, the perilla secondary amine derivative and the like have better weeding activity, and partial compound activity is better than that of herbicide glyphosate and diuron (Zhu, journal of Agricultural and Food Chemistry,2016,64 (51), 9702-9707;Zhu,Industrial Crops&Products,2018,115,111-116; xu, journal of Agricultural and Food Chemistry,2020,68,11829-11838; dong, new Journal of Chemistry,2020,44,8280-8288.). For example N- (4-fluorobenzyl) -3-p ∈ ->IC of alkene-1-amine (5) on barnyard grass root growth 50 The value was about 7mg/L.
Previous studies have focused primarily onAlkene and p->The derivatization of alkanes as parent structures has not been implicated in the herbicidal activity of ring-opened monoterpenes and their derivatives. Linalool (6) is a chain monoterpene enol with mugwort aroma, is commonly used in the flavor industry, and is used in the pharmaceutical and pesticide industry because of the insecticidal and antibacterial effects. Tetrahydrolinalool is a chain monoterpene amine compound, can be prepared from linalool through hydrogenation, ritter reaction and alkaline hydrolysis, and is an organic reaction intermediate (Zhu, industrial caps)&Products,2018,115,111-116; king, forest chemical and process, 2018,38 (6), 59-66.). Earlier researches show that tetrahydrolinalyl schiff base compounds have strong ryegrass growth inhibition activity, but imino groups in schiff base structures are unstable and are easy to decompose in the weeding application process, so that the pesticide effect is reduced, and therefore, the imino groups are reduced to more stable secondary amino groups, which is beneficial to improving the weeding activity.
The application of the invention provides a novel plant source weeding active substance tetrahydrolinalyl secondary amine compound, a preparation method thereof and application of related compounds in the weeding field, and the application is compared with the previous research results to prove that the compound contains the para-amino groupAlkyl skeleton and no p->The influence of the alkyl skeleton structure on the herbicidal activity is compared with the herbicidal activity of tetrahydrolinalool amine Schiff base and secondary amine derivatives, and based on the herbicidal activity, the herbicidal active substance with novel structure and better activity is designed and synthesized.
Disclosure of Invention
The invention discloses preparation and weeding application of a novel plant source weeding active substance tetrahydrolinalyl secondary amine compound, which aims to solve the defects that a synthetic herbicide is high in toxicity and difficult to biodegrade. The invention takes para-tetrahydrolinalool amine and aldehyde as raw materials, and the related tetrahydrolinalool Schiff base compound is prepared by directly reducing reactants without purification, drying and distilling under reduced pressure after fully reacting in a polar organic solvent.
The technical scheme of the invention is as follows: a tetrahydrolinalool secondary amine compound has the following structural general formula:
in the general formula I, R is R' is any one of hydrogen, methyl, trifluoromethyl, methoxy, methylthio or halogen.
The compound of the general formula I is prepared by fully reacting tetrahydrolinalool and aldehyde serving as raw materials in a polar organic solvent at a certain temperature, then directly reducing the raw materials by hydride, and performing post-treatment on a reaction solution, wherein the aldehyde is benzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde, 3, 4-difluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2, 4-dichlorobenzaldehyde, 2, 6-dichlorobenzaldehyde, 4-bromobenzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldehyde, p-methylthiobenzaldehyde, 2-trifluoromethyl benzaldehyde, 4-trifluoromethyl benzaldehyde, 2, 4-bistrifluoromethyl benzaldehyde, pyridine-2-formaldehyde, pyridine-3-formaldehyde, pyridine-4-formaldehyde, thiophene-2-formaldehyde, furan-2-formaldehyde, 5-methyl-furan-2-formaldehyde, 5-bromo-furan-2-formaldehyde, tetrahydroperillaldehyde and terephthalaldehyde.
The molar ratio of the tetrahydrolinalool amine to the aldehyde is 1:1-5.
The reaction temperature of the tetrahydrolinalool and the aldehyde is between 0 and 100 ℃. The reaction time is 1-72 h.
The polar organic solvent is one or a mixture of several of methanol, ethanol, tetrahydrofuran, dimethylformamide and dimethyl sulfoxide.
The hydride reducing agent is any one of sodium borohydride, potassium borohydride and lithium aluminum hydride. The molar weight ratio of the tetrahydrolinalool amine to the reducing agent is calculated to be 1:1-10.
The reaction temperature of the reduction reaction is between-20 and 60 ℃, and the reaction time of the reduction reaction is between 1 and 24 hours.
The post-treatment specifically refers to that the reaction solution is dried by anhydrous sodium sulfate, filtered and distilled under reduced pressure to obtain a crude product of tetrahydrolinalyl schiff base compounds, and the crude product is recrystallized or subjected to silica gel column chromatography to obtain a pure product.
The tetrahydrolinalool secondary amine compound is applied as an active ingredient of herbicide.
The tetrahydrolinalool secondary amine compound is applied as an active ingredient of herbicide aiming at ryegrass.
Advantageous effects
1. The tetrahydrolinalool secondary amine compound disclosed by the invention is a novel natural product derivative, and has the characteristics of low toxicity, high safety, environmental friendliness and the like;
2. the invention has simple synthesis process, mild condition, fast reaction rate, high product yield, wide substrate applicability and easy mass production.
3. The tetrahydrolinalool secondary amine compound disclosed by the invention has excellent herbicidal activity on ryegrass stem and root growth.
Drawings
FIG. 1 is a schematic diagram of N-benzyl-tetrahydrolinalool amine 1 H NMR chart;
FIG. 2 is a schematic diagram of N- (4-fluorobenzyl) -tetrahydrolinalool amine 1 H NMR chart;
FIG. 3 is a schematic diagram of N- (4-chlorobenzyl) -tetrahydrolinalool amine 1 H NMR chart;
FIG. 4 is a schematic illustration of N- (p-methylbenzyl) -tetrahydrolinalool amine 1 H NMR chart;
FIG. 5 is a schematic diagram of N- (2-trifluoromethylbenzyl) -tetrahydrolinalool amine 1 H NMR chart;
FIG. 6 is a schematic diagram of N- (pyridin-3-ylmethylene) -tetrahydrolinalool amine 1 H NMR chart;
FIG. 7 is a schematic diagram of N, N' -bistetrahydrolinalyl-1, 4-benzyl diamine 1 H NMR chart.
Detailed Description
Analysis method
Analyzing the product by adopting a gas chromatography peak area normalization method, wherein the analysis conditions are as follows: shimadzu GC-2014AF, carrier gas N 2 The pressure is 0.6MPa, the air pressure is 0.6MPa, H 2 The pressure is 0.6MPa, the temperature programming is adopted, and the temperature programming is as follows: 70 ℃ (hold 2min, rate 3 ℃/min) →130 ℃ (hold 0min, rate 10 ℃/min) →270 ℃ (hold 2 min).
The method comprises the steps of taking tetrahydrolinalool and aldehyde as raw materials, carrying out condensation reaction in a polar organic solvent, adding a hydride reducing agent in batches after the raw materials are fully reacted, quenching reaction liquid by distilled water, extracting by methylene dichloride, drying by anhydrous sodium sulfate, filtering, distilling under reduced pressure to obtain a crude tetrahydrolinalool secondary amine compound, recrystallizing or carrying out silica gel column chromatography to obtain a target product pure product, measuring the growth damage condition of roots and stems of ryegrass under the culture of tetrahydrolinalool secondary amine compounds with different concentrations by adopting a culture dish seed germination method, and evaluating the weeding activity of the product. The structural general formula of the tetrahydrolinalool secondary amine compound is as follows:
in the general formula I, R is R' is any one of hydrogen, methyl, trifluoromethyl, methoxy, methylthio or halogen.
Tetrahydrolinalool is purchased from Shanghai A Ding Huaxue reagent limited company, tetrahydrolinalool is obtained by taking tetrahydrolinalool as a raw material through Ritter reaction and alkaline hydrolysis, and the tetrahydrolinalool crude product is distilled to obtain the tetrahydrolinalool with the purity of 97 percent.
The specific synthesis steps are as follows:
adding tetrahydrolinalool into a three-neck flask containing a polar organic solvent, adding aldehyde under magnetic stirring, transferring the flask into an ice bath after the raw materials are fully reacted, adding a reducing agent in batches, continuing to react for a certain time at a certain temperature after the material is added, drying reaction liquid anhydrous sodium sulfate after the reaction is finished, filtering, and distilling under reduced pressure to obtain a tetrahydrolinalyl Schiff base compound crude product, and recrystallizing or performing silica gel column chromatography to obtain a pure product. Wherein the molar ratio of tetrahydrolinalool to aldehyde is 1:1-5, the condensation reaction temperature is 0-100 ℃, and the reaction time is 1-72 h; the polar organic solvent is one or a mixture of several of methanol, ethanol, tetrahydrofuran, dimethylformamide and dimethyl sulfoxide; the hydride is any one of sodium borohydride, potassium borohydride and lithium aluminum hydride; the mole ratio of the raw materials to the hydride is 1:1-10 (calculated by the mole ratio of tetrahydrolinalool amine to the reducer); the reaction temperature of the reduction reaction is between-20 and 60 ℃; the reaction time of the reduction reaction is 1-24 h.
The tetrahydrolinalool secondary amine compound is applied as an active ingredient of herbicide.
The tetrahydrolinalool secondary amine compound is applied as an active ingredient of herbicide aiming at ryegrass. The herbicide activity test method is as follows:
accurately weighing 0.5mmol of tetrahydrolinalool secondary amine compound, respectively dissolving with 1mL of DMF, dropwise adding three drops of Tween 80, fully dissolving, transferring to a 100mL volumetric flask, and diluting to scale with distilled water to obtain a solution with the concentration of 5mmol/L as a mother liquor. A series of concentrations (2.5 mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L, 0.0049mmol/L, and the concentration of DMF and Tween 80 in the dilution was the same as that in the mother liquor) were prepared by the double dilution method.
The ryegrass seeds are respectively placed in an incubator at 28 ℃ and soaked in a proper amount of distilled water for 15 hours. 2 pieces of filter paper are spread in a culture dish, 7mL of sample solution with the corresponding concentration of the compound is added, 7mL of diluent is added as a control, and each treatment is repeated three times. 10 seeds are added into each culture dish, and the culture dishes are placed into a climatic incubator for non-illumination culture for 120 hours under the conditions of the temperature of 28 ℃ and the relative humidity of 70-80 percent. After the cultivation is finished, the root length and the stem length of ryegrass are measured, and the root length and the stem length inhibition rate (y) of the tetrahydrolinalool secondary amine compound on ryegrass seeds is calculated.
Wherein: y is the inhibition (%) of root length or stem length, x is the inhibition (%) 0 Root length or stem length (mm), x of control group 1 Root length or stem length (mm) for compound treatment.
Example 1
3.24g (20 mmol, 97%) tetrahydrolinalool was added to a three-necked flask containing 20mL of ethanol, and 2.12g (20 mmol) of benzaldehyde was added under magnetic stirring and reacted at room temperature for 48h. Then the flask was transferred to an ice-water bath, 3.04g (60 mmol) of sodium borohydride was added under magnetic stirring in 3 portions, each time at 30min intervals, and after the reaction was completed at room temperature after the addition was completed, anhydrous sodium sulfate was added for drying, filtration and distillation under reduced pressure to remove the solvent, 3.9g of N-benzyl-tetrahydrolinalool amine was obtained, and the yield was 75.7%.
Accurately weighing 1mmol of N-benzyl-tetrahydrolinalool, dissolving with 1mL of DMF, dropwise adding three drops of Tween 80, transferring to a 100mL volumetric flask after full dissolution, and diluting to a scale with distilled water to obtain a solution with the concentration of 10mmol/L as a mother liquor. The double dilution method is adopted, and a series of test solutions with the concentration are prepared by using the diluent. The ryegrass seeds are placed in a constant temperature box at 28 ℃ and soaked in a proper amount of distilled water for 15 hours. 2 pieces of filter paper are spread in a culture dish, 7mL of sample solution with the corresponding concentration of the compound is added, 7mL of diluent is added as a blank control, and each treatment is repeated three times. 10 seeds are added into each culture dish, and the culture dishes are placed into a climatic incubator for non-illumination culture for 120 hours under the conditions of the temperature of 28 ℃ and the relative humidity of 70-80 percent.
The inhibition ratios of the N-benzyl-tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.7%, 85.1%, 60.1%, 49.4%, 38.0%, 19.8%, 16.4%, 9.4%, and the inhibition rates on root length are respectively: 100.0%, 87.4%, 58.4%, 42.8%, 35.2%, 25.3%, 23.9%, 11.8%. (the inhibition rates of the glyphosate solutions of 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L on ryegrass seed stem length are respectively 100.0%, 99.5%, 93.6%, 82.3%, 55.0%, 40.2%, 37.8%, 22.4%, 11.5% and 9.5%, and root length is respectively 100.0%, 95.7%, 87.8%, 76.1%, 68.6%, 57.8%, 27.2%, 19.5% and 12.3%).
Example 2
The procedure of example 1 was followed except that the starting aldehyde was 2-fluorobenzaldehyde, to give 5.0g of N- (2-fluorobenzyl) -tetrahydrolinalool amine in 90.0% yield. The inhibition ratios of the N- (2-fluorobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.6%, 89.7%, 58.9%, 42.5%, 32.7%, 18.1%, 14.6%, 10.4%, the inhibition rates for root length are respectively: 100.0%, 93.9%, 65.6%, 44.9%, 33.4%, 26.1%, 20.8%, 18.2%.
Example 3
The procedure of example 1 was followed except that the starting aldehyde was 4-fluorobenzaldehyde, to give 5.0g of N- (4-fluorobenzyl) tetrahydrolinalool amine in 90.0% yield. The inhibition ratios of the N- (4-fluorobenzyl) tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.6%, 95.0%, 71.6%, 51.0%, 46.1%, 28.9%, 21.1%, 18.3%, the inhibition rates for root length are respectively: 100.0%, 97.2%, 77.1%, 59.7%, 51.2%, 43.6%, 38.2%, 30.3%.
Example 4
The procedure of example 1 was repeated except for using 3, 4-difluorobenzaldehyde as the starting aldehyde to give 5.8g of N- (3, 4-difluorobenzyl) -tetrahydrolinalool amine in 97.3% yield. The inhibition ratios of the N- (3, 4-difluorobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively: 100.0%, 99.7%, 98.0%, 86.5%, 48.5%, 20.1%, 18.5%, 14.6%, 8.1%, and inhibition ratios to root length are respectively: 100.0%, 99.5%, 87.4%, 59.3%, 31.1%, 23.4%, 19.9%, 15.3%.
Example 5
The procedure of example 1 was followed except that the starting aldehyde was 2-chlorobenzaldehyde, to give 5.3g of N- (2-chlorobenzyl) -tetrahydrolinalool amine in 90.9% yield. The inhibition ratios of the N- (2-chlorobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 96.9%, 70.8%, 59.6%, 31.3%, 22.4%, 11.2%, 2.7%, and the inhibition rates for root length are respectively: 100.0%, 99.4%, 77.1%, 63.3%, 39.4%, 21.5%, 19.6%, 13.7%.
Example 6
The procedure of example 1 was followed except that the starting aldehyde was 3-chlorobenzaldehyde, to give 5.3g of N- (3-chlorobenzyl) -tetrahydrolinalool amine in 90.2% yield. The inhibition ratios of the N- (3-chlorobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 94.2%, 63.7%, 50.2%, 30.0%, 16.8%, 13.1%, 7.2%, and the inhibition rates for root length are respectively: 100.0%, 98.7%, 78.6%, 53.4%, 37.8%, 30.9%, 17.2%, 12.2%.
Example 7
The procedure of example 1 was followed except that the starting aldehyde was 4-chlorobenzaldehyde, to give 4.3g of N- (4-chlorobenzyl) -tetrahydrolinalool amine in 80.0% yield. The inhibition ratios of the N- (4-chlorobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.7%, 90.8%, 56.3%, 36.9%, 29.6%, 17.0%, 14.4%, 6.8%, and inhibition ratios to root length are respectively: 100.0%, 99.8%, 99.2%, 78.5%, 46.1%, 34.8%, 17.5%, 9.8%, 6.8%.
Example 8
The procedure of example 1 was repeated except for using 2, 4-dichlorobenzaldehyde as the starting material to give 5.6g of N- (2, 4-dichlorobenzyl) -tetrahydrolinalool amine in 85.6% yield. The inhibition ratios of the N- (2, 4-dichlorobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.3%, 96.2%, 88.8%, 69.5%, 47.9%, 28.8%, 21.4%, 15.7%, 10.2%, the inhibition rates for root length are respectively: 100.0%, 98.9%, 94.5%, 77.5%, 51.4%, 32.5%, 20.8%, 17.9%, 12.6%.
Example 9
The procedure of example 1 was repeated except for using 2, 6-dichlorobenzaldehyde as the starting material to give 5.8g of N- (2, 6-dichlorobenzyl) -tetrahydrolinalool amine in a yield of 87.9%. The inhibition ratios of the N- (2, 6-dichlorobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.3%, 96.1%, 81.5%, 68.7%, 36.6%, 23.4%, 12.3%, 13.1%, 7.5%, and the inhibition rates for root length are respectively: 100.0%, 98.2%, 86.9%, 76.0%, 45.7%, 36.5%, 25.9%, 20.1%, 17.4%.
Example 10
The procedure of example 1 was followed except that the starting aldehyde was 4-bromobenzaldehyde, to give 4.8g of N- (4-bromobenzyl) -tetrahydrolinalool amine in 71.0% yield. The inhibition ratios of the N- (4-bromobenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 98.9%, 89.6%, 64.7%, 53.3%, 28.7%, 18.1%, 17.4%, 13.8%, and inhibition ratios to root length are respectively: 100.0%, 99.1%, 90.3%, 67.9%, 44.9%, 41.9%, 26.4%, 17.0%.
Example 11
The procedure of example 1 was followed except that the starting aldehyde was p-methylbenzaldehyde, to give 4.0g of N- (p-methylbenzyl) -tetrahydrolinalool amine in 72.3% yield. The inhibition ratios of the N- (p-methylbenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.6%, 83.9%, 56.8%, 53.3%, 36.5%, 25.3%, 19.9%, 14.0%, the inhibition rates for root length are respectively: 100.0%, 95.2%, 62.6%, 40.7%, 31.2%, 23.7%, 14.8%, 12.1%.
Example 12
The procedure of example 1 was followed except that the starting aldehyde was p-methoxybenzaldehyde, to give 3.8g of N- (p-methoxybenzyl) -tetrahydrolinalool amine in 67.9% yield. The inhibition ratios of the N- (p-methoxybenzyl) -tetrahydrolinalool amine solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 95.3%, 75.2%, 53.0%, 39.7%, 22.2%, 16.4%, 14.6%, 13.6%, and inhibition ratios to root length are respectively: 100.0%, 98.2%, 80.5%, 55.5%, 33.7%, 25.9%, 18.7%, 16.8%, 17.3%.
Example 13
The procedure of example 1 was repeated except that the starting aldehyde was p-mercaptomethylbenzaldehyde to give 5.4g of N- (p-methylthiobenzyl) -tetrahydrolinalool amine in 87.5% yield. The inhibition rates of the N- (p-mercaptomethylbenzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L on ryegrass seed stem length are respectively as follows: 100.0%, 99.6%, 92.3%, 84.6%, 62.6%, 47.2%, 32.1%, 16.2%, 10.6%, 9.9%, the inhibition rates for root length are respectively: 100.0%, 96.3%, 78.8%, 43.8%, 25.2%, 18.4%, 13.9%, 15.3%.
Example 14
The procedure of example 1 was repeated except for using 2-trifluoromethylbenzaldehyde as the starting aldehyde to give 5.1g of N- (2-trifluoromethylbenzyl) -tetrahydrolinalool amine in a yield of 78.8%. The inhibition ratios of the N- (2-trifluoromethyl benzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.6%, 96.0%, 71.8%, 51.1%, 35.1%, 18.6%, 19.2%, 12.3%, the inhibition rates for root length are respectively: 100.0%, 98.9%, 7.4%, 53.0%, 31.6%, 27.4%, 18.9%, 12.6%.
Example 15
The procedure of example 1 was repeated except for using 4-trifluoromethylbenzaldehyde as the starting aldehyde to give 4.2g of N- (4-trifluoromethylbenzyl) -tetrahydrolinalool amine in a yield of 78.0%. The inhibition ratios of the N- (4-trifluoromethyl benzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.5%, 97.3%, 75.8%, 53.0%, 31.9%, 27.6%, 23.4%, 17.4%, and inhibition ratios to root length are respectively: 100.0%, 99.3%, 85.1%, 62.2%, 41.1%, 33.3%, 24.8%, 18.5%.
Example 16
The procedure of example 1 was repeated except for using 2, 4-bistrifluoromethylbenzaldehyde as the starting material to give 5.2g of N- (2, 4-bistrifluoromethylbenzyl) -tetrahydrolinalool amine in 77.2% yield. The inhibition rates of the N- (2, 4-bistrifluoromethyl benzyl) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L on ryegrass seed stem length are respectively as follows: 100.0%, 99.0%, 95.0%, 93.2%, 68.5%, 36.3%, 21.1%, 12.8%, 16.5%, 14.6%, and inhibition ratios to root length are respectively: 100.0%, 98.8%, 95.8%, 93.2%, 67.3%, 39.8%, 28.4%, 17.8%, 13.5%, 12.2%.
Example 17
The procedure of example 1 was followed except that the starting aldehyde was pyridine-2-carbaldehyde to give 3.5g of N- (pyridine-2-methylene) -tetrahydrolinalool amine in 67.9% yield. The inhibition ratios of the N- (pyridine-2-methylene) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 98.9%, 84.5%, 61.5%, 50.7%, 41.2%, 40.3%, 28.7%, 26.1%, 16.7% inhibition ratios to root length are respectively: 100.0%, 91.7%, 71.3%, 54.7%, 42.5%, 40.6%, 35.0%, 29.2%, 16.7%.
Example 18
The procedure of example 1 was followed except that the starting aldehyde was pyridine-3-carbaldehyde to give 4.3g of N- (pyridine-3-methylene) -tetrahydrolinalool amine in 85.7% yield. The inhibition ratios of the N- (pyridine-3-methylene) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 97.0%, 73.9%, 60.0%, 53.4%, 36.4%, 28.9%, 18.0%, 16.1%, 9.7%, and inhibition ratios to root length are respectively: 100.0%, 99.7%, 79.9%, 56.5%, 46.4%, 32.5%, 30.6%, 22.1%, 20.3%, 16.6%.
Example 19
The procedure of example 1 was repeated except for using pyridine-4-carbaldehyde as the starting material to give 4.5g of N- (pyridine-4-methylene) -tetrahydrolinalool amine in a yield of 87.0%. The inhibition ratios of the N- (pyridine-4-methylene) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 98.7%, 78.2%, 52.7%, 40.9%, 41.5%, 30.2%, 14.9%, 12.5%, 7.6%, and the inhibition rates for root length are respectively: 100.0%, 99.4%, 88.2%, 53.4%, 43.6%, 42.1%, 34.5%, 23.2%, 21.7%, 20.2%.
Example 20
The procedure of example 1 was followed except that the starting aldehyde was thiophene-2-carbaldehyde to give 3.9g of N- (thiophene-2-methylene) -tetrahydrolinalool amine in 76.9% yield. The inhibition ratios of the N- (thiophene-2-methylene) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 99.6%, 83.7%, 51.3%, 41.4%, 29.8%, 19.3%, 15.9%, 8.0%, and inhibition ratios to root length are respectively: 100.0%, 98.2%, 89.5%, 46.8%, 42.7%, 31.9%, 23.9%, 23.3%, 21.1%.
Example 21
The procedure of example 1 was repeated except for using furan-2-carbaldehyde as the starting material to give 3.9g of N- (furan-2-methylene) -tetrahydrolinalool amine in 79.9% yield. The inhibition ratios of the N- (furan-2-methylene) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 96.9%, 74.2%, 45.0%, 35.0%, 32.8%, 23.9%, 17.1%, 13.9%, the inhibition rates for root length are respectively: 100.0%, 98.9%, 81.9%, 51.7%, 42.6%, 38.6%, 33.2%, 27.9%, 21.9%.
Example 22
The procedure of example 1 was repeated except for using 5-methyl-furan-2-carbaldehyde as a starting material to give 5.0g of N- (5-methyl-furan-2-methylene) -tetrahydrolinalool amine in 96.3% yield. The inhibition rates of the N- (5-methyl-furan-2-methylene) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L on ryegrass seed stem length are respectively as follows: 100.0%, 98.5%, 81.9%, 48.1%, 36.6%, 30.4%, 26.9%, 19.1%, 15.1% inhibition ratios to root length are respectively: 100.0%, 99.8%, 85.2%, 51.5%, 36.4%, 31.4%, 28.3%, 20.4%, 18.1%.
Example 23
The procedure of example 1 was repeated except for using 5-bromo-furan-2-carbaldehyde as the starting material to give 5.9g of N- (5-bromo-furan-2-methylene) -tetrahydrolinalool amine in 89.2% yield. The inhibition rates of the N- (5-bromo-furan-2-methylene) -tetrahydrolinalool solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L on ryegrass seed stem length are respectively as follows: 100.0%, 92.8%, 72.4%, 59.5%, 47.9%, 37.1%, 27.3%, 17.4%, the inhibition rates for root length are respectively: 100.0%, 96.7%, 75.2%, 54.5%, 41.1%, 34.4%, 21.5%, 17.3%.
Example 24
The procedure of example 1 was repeated except that the starting aldehyde was tetrahydroperillaldehyde to give 3.3g of N- (tetrahydroperillyl) tetrahydrolinalool in 43.7% yield. The inhibition ratios of the N- (tetrahydropurple perilla) -tetrahydrolinalool amine solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 100.0%, 98.1%, 73.8%, 49.7%, 32.4%, 28.2%, 14.0%, 5.0%, and inhibition ratios to root length are respectively: 100.0%, 90.9%, 69.5%, 50.5%, 38.7%, 22.4%, 11.7%.
Example 25
The procedure of example 1 was repeated except that the raw material aldehyde was terephthalaldehyde, to obtain 4.5g of N, N' -dibenzyl-tetrahydrolinalool amine, and the yield was 98.0%. The inhibition ratios of the N, N' -dibenzyl-tetrahydrolinalool amine solution with 2.5mmol/L, 1.25mmol/L, 0.625mmol/L, 0.3125mmol/L, 0.1563mmol/L, 0.0781mmol/L, 0.0391mmol/L, 0.0195mmol/L, 0.0098mmol/L and 0.0049mmol/L to ryegrass seed stem length are respectively as follows: 99.1%, 97.5%, 95.9%, 84.0%, 60.2%, 44.9%, 35.6%, 25.7%, 17.8%, 15.5%, the inhibition rates for root length are respectively: 100.0%, 96.9%, 84.5%, 53.8%, 40.5%, 30.6%, 23.0%, 18.8%.
Example 26
The procedure is as in example 1 with the exception that the molar ratio of tetrahydrolinalool to 4-fluorobenzaldehyde is 1:2, with a yield of 91%.
Example 27
The procedure of example 1 was followed except that the reaction temperature of tetrahydrolinalool and 4-fluorobenzaldehyde was 0℃to give a yield of 80%.
Example 28
The procedure of example 1 was followed except that the reaction temperature of tetrahydrolinalool and 4-fluorobenzaldehyde was 70℃to give a yield of 93%.
Example 29
The procedure of example 1 was followed except that the reaction solvent of tetrahydrolinalool and 4-fluorobenzaldehyde was acetone, to give a 90% yield.
Example 30
The procedure was followed in example 1 with the exception of 0.5h of reaction time and 72% yield.
Example 31
The procedure of example 1 was followed except that the reaction time was 72 hours, to give 89% of a yield.

Claims (10)

1. A tetrahydrolinalool secondary amine compound is characterized by having the following structural general formula:
in the general formula I, R is R' is any one of hydrogen, methyl, trifluoromethyl, methoxy, methylthio or halogen.
2. The method for preparing the tetrahydrolinalool secondary amine compound according to claim 1 is characterized in that the compound of the general formula I takes tetrahydrolinalool amine and aldehyde as raw materials, and is obtained by fully reacting in a polar organic solvent at a certain temperature, directly reducing the reaction solution by hydride, and then carrying out post-treatment on the reaction solution, wherein the aldehyde is benzaldehyde, 2-fluorobenzaldehyde, 4-fluorobenzaldehyde, 3, 4-difluorobenzaldehyde, 2-chlorobenzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2, 4-dichlorobenzaldehyde, 2, 6-dichlorobenzaldehyde, 4-bromobenzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldehyde, p-methylthiobenzaldehyde, 2-trifluoromethyl benzaldehyde, 4-trifluoromethyl benzaldehyde, 2, 4-bistrifluoromethylbenzaldehyde, pyridine-2-formaldehyde, pyridine-3-formaldehyde, pyridine-4-formaldehyde, thiophene-2-formaldehyde, furan-2-formaldehyde, 5-methyl-furan-2-formaldehyde, 5-bromo-furan-2-formaldehyde, tetrahydroperilla aldehyde and p-benzaldehyde.
3. The process for preparing secondary tetrahydrolinalool amines according to claim 2, wherein the molar ratio of tetrahydrolinalool amine to aldehyde is between 1:1 and 5.
4. The method for preparing tetrahydrolinalool secondary amines according to claim 2, wherein the reaction temperature of tetrahydrolinalool amine and aldehyde is between 0 and 100 ℃; the reaction time is 1-72 h.
5. The method for preparing tetrahydrolinalool secondary amine compounds according to claim 2, wherein the polar organic solvent is one or a mixture of several of methanol, ethanol, tetrahydrofuran, dimethylformamide and dimethyl sulfoxide.
6. The method for preparing tetrahydrolinalool secondary amine compound according to claim 2, characterized in that the hydride reducing agent is any one of sodium borohydride, potassium borohydride and lithium aluminum hydride; the molar weight ratio of tetrahydrolinalool amine to the reducing agent is 1:1-10.
7. The method for preparing tetrahydrolinalool secondary amine compounds according to claim 2, characterized in that the reaction temperature of the reduction reaction is between-20 and 60 ℃ and the reaction time of the reduction reaction is between 1 and 24 hours.
8. The method for preparing tetrahydrolinalool secondary amine compounds according to claim 2, wherein the post-treatment specifically means that the reaction solution is dried by anhydrous sodium sulfate, filtered and distilled under reduced pressure to obtain crude tetrahydrolinalool secondary amine compounds, and then recrystallized or subjected to silica gel column chromatography to obtain pure products.
9. The use of tetrahydrolinalool secondary amines according to claim 1 as herbicide active ingredients.
10. Use of the tetrahydrolinalool secondary amines of claim 1 as herbicide active ingredient against ryegrass.
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