Furan ring-containing ester compound as well as preparation method and application thereof

Abstract

The invention relates to a compound and new application thereof, and discloses a furan ring-containing ester compound and a preparation method and application thereof, 2-furancarboxylic acid or 3-furancarboxylic acid and halogenated olefin or halogenated alkyne compound are used as raw materials, tetrabutylammonium bromide is used as a catalyst, reflux reaction is carried out in acetonitrile at 80 DEG C in the presence of potassium carbonate, and the furan ring-containing ester compound is obtained. The ester compound containing the furan ring is obtained. A one-pot preparation method is adopted, and the synthesis method is simple, green and efficient; the obtained compound is an environment-friendly compound, has no pollution to the environment in the application process, and has the advantages of broad spectrum and high efficiency.

Description

Technical Field

[0001] The present invention relates to a class of compounds and their new uses, and particularly to an ester compound containing a furan ring, its preparation method and applications. Background Art

[0002] Furoate esters are a class of key organic compounds with high chemical reactivity and wide application scope. For example, 2-furoate esters and methyl 3-furoate have significant application values in multiple fields such as organic synthesis, perfume manufacturing, and pharmaceutical intermediates. However, there is no literature report on the application of furoate ester compounds in nematicides.

[0003] In particular, 2-furoic acid and 3-furoic acid exhibit significant nematicidal activities, which can effectively inhibit the activities of root-knot nematodes, reduce their motility and egg hatching rate, thereby killing root-knot nematodes. These compounds have a significant inhibitory effect on the infectivity of host plants (such as cucumbers) under sandy soil conditions and have no obvious toxicity to plant growth, showing the development potential as a new type of nematicide. In addition, compounds containing unsaturated olefin (alkyne) groups are also considered as an important class of nematicidal active compounds. For example, compounds containing a trifluorobutenyl group have broad application prospects in the field of nematicides, characterized by high efficiency, low toxicity, and easy degradation. Compounds such as ethoprophos and flupyradifurone have shown good nematicidal activities and excellent environmental compatibility. Coupling furoic acid with unsaturated olefin (alkyne) is expected to produce a synergistic effect between the two.

[0004] Therefore, it is of great research value to study and develop unsaturated ester compounds containing a furan ring and explore their nematicidal activities to find safer and more effective means to combat root-knot nematodes. Summary of the Invention

[0005] To solve the above technical problems, the present invention provides an ester compound containing a furan ring, its preparation method and applications, so as to achieve the purpose of providing a safer and more effective nematicide.

[0006] To achieve the above purpose, the technical solution of the present invention is as follows:

[0007] An ester compound containing a furan ring, whose structural formula is shown as formula (I) or (II):

[0008]

[0009] In the formula, R 1 is selected from C5-C7 alkenyl, C3-C4 alkynyl, trifluorobutenyl.

[0010] In the above scheme, R1 Selected from one of the following structures:

[0011]

[0012] A method for preparing an ester compound containing a furan ring as described above, reacting 2-furoic acid or 3-furoic acid with a haloalkene or haloalkyne compound, to obtain the ester compound containing a furan ring shown in formula (I) or (II).

[0013] In the above solution, using 2-furoic acid or 3-furoic acid and a haloalkene or haloalkyne compound as raw materials, tetrabutylammonium bromide as a catalyst, refluxing and reacting in acetonitrile at 80 °C in the presence of potassium carbonate, to obtain the ester compound containing a furan ring shown in formula (I) (II).

[0014] In a further technical solution, the molar ratio of 2-furoic acid or 3-furoic acid, haloalkene or haloalkyne compound, potassium carbonate, and tetrabutylammonium bromide is 0.8 - 1.2:1.2 - 1.8:1.6 - 2.4:0.13 - 0.17.

[0015] An application of an ester compound containing a furan ring as described above in the preparation of an agricultural nematicide preparation for killing root-knot nematodes.

[0016] In a further technical solution, the root-knot nematode is Meloidogyne incognita.

[0017] Through the above technical solution, an ester compound containing a furan ring provided by the present invention, its preparation method and application have the following beneficial effects:

[0018] The present invention uses 2-furoic acid or 3-furoic acid and a haloalkene or haloalkyne compound as raw materials, tetrabutylammonium bromide as a catalyst, refluxing and reacting in acetonitrile at 80 °C in the presence of potassium carbonate, and is prepared by a one-pot method. The synthesis method is simple, green and efficient; the obtained compound is an environmentally friendly compound, has no pollution to the environment during the application process, and has the advantages of broad spectrum and high efficiency. Specific Embodiments

[0019] The technical solutions in the embodiments of the present invention will be described clearly and completely below.

[0020] The present invention provides a method for preparing an ester compound containing a furan ring, and the specific embodiments are as follows:

[0021] The processes and methods not described in detail in the following embodiments are conventional methods well known in the art. The reagents used in the embodiments are all of analytical grade or chemical grade, and can be purchased commercially or prepared by methods well known to those of ordinary skill in the art. The following embodiments have all achieved the purpose of the present invention.

[0022] Table 1 below lists some compounds represented by formula (I) of the present invention:

[0023] Table 1

[0024]

[0025] Table 2 below lists some compounds represented by formula (II) of the present invention:

[0026] Table 2

[0027] Compound <![CDATA[R 1 > Molecular weight B-1 <![CDATA[CH 2 CH 2 CH 2 CH 2 CHCH 2 > 222 B-2 <![CDATA[CH 2 CH 2 CH 2 CH 2 CH 2 CHCH 2 > 208 B-3 <![CDATA[CH 2 CH 2 CFCF 2 > 220

[0028] Example 1

[0029] Synthesis of Propyl 2-ethynylfuran-2-carboxylate (A-1)

[0030] Weigh 2-furoic acid (5 mmol), 3-bromopropyne (7.5 mmol), potassium carbonate (10 mmol), and tetrabutylammonium bromide (0.1 g) into a 150 mL round-bottom flask, add 30 mL of toluene, and reflux and stir at 80 °C for 10 h. Monitor the reaction by TLC (ethyl acetate: petroleum ether 1:20) until the reaction is complete. After the reaction is completed, filter the reaction solution, wash it 3 times with water (100 mL), separate the organic layer, dry the organic layer with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain the crude product, a yellow liquid. Purify and separate it using a silica gel chromatography column (ethyl acetate: petroleum ether 1:100 as the eluent, silica gel with a mesh size of 100-140 produced by the branch factory of Qingdao Marine Biological Chemical Factory) to obtain propyl 2-ethynylfuran-2-carboxylate, a white liquid, with a yield of 74.8%.

[0031] The reaction equation is as follows:

[0032]

[0033] Characterize the obtained product, and the results are as follows: 1 H NMR (600 MHz, Chloroform-d) δ 8.06 (d, J = 3.7 Hz, 1H), 7.45 - 7.42 (m, 1H), 6.78 - 6.75 (m, 1H), 4.87 - 4.81 (m, 2H), 2.53 - 2.48 (m, 1H). 13 C NMR (151 MHz, Chloroform-d) δ 162.28, 148.33, 143.97, 118.63, 109.89, 77.69, 75.12, 52.02.

[0034] Example 2

[0035] Synthesis of Octyl 3-formylfuran-5-ene-1-carboxylate (B-1)

[0036] Weigh 3-furoic acid (5 mmol), 6-bromo-1-octene (7.5 mmol), potassium carbonate (10 mmol), and tetrabutylammonium bromide (0.1 g) into a 150 mL round-bottom flask. Add 30 mL of toluene and reflux and stir at 80 °C for 10 h. Monitor the reaction by TLC (ethyl acetate: petroleum ether = 1:20) until the reaction is complete. After the reaction is completed, filter the reaction solution, wash it 3 times with water (100 mL), separate the organic layer by liquid separation, dry the organic layer with anhydrous magnesium sulfate, filter, and rotary evaporate to obtain the crude product, a brown liquid. Purify and separate it using a silica gel chromatography column (ethyl acetate: petroleum ether = 1:100 as the eluent, 100 - 140 mesh silica gel produced by the branch factory of Qingdao Marine Biological Chemical Factory) to obtain 3-furoyl-5-octen-1-ol, a pale yellow liquid, with a yield of 51.8%.

[0037] The reaction equation is as follows:

[0038]

[0039] Characterize the obtained product, and the results are as follows: 1 H NMR (500 MHz, Chloroform-d) δ 7.56 (dd, J = 1.6, 0.8 Hz, 1H), 7.16 (dd, J = 3.5, 0.7 Hz, 1H), 6.49 (dd, J = 3.5, 1.7 Hz, 1H), 5.79 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 4.98 (dd, J = 17.1, 2.0 Hz, 1H), 4.95 - 4.90 (m, 1H), 4.29 (t, J = 6.8 Hz, 2H), 2.06 - 2.01 (m, 2H), 1.76 - 1.70 (m, 2H), 1.38 (dq, J = 15.3, 5.1, 4.4 Hz 6H). 13 C NMR (126 MHz, Chloroformd) δ 158.83, 146.16, 144.86, 138.90, 117.67, 114.32,

[0040] 111.75, 65.03, 33.65, 28.81 - 28.55 (m), 25.74.

[0041] At the same time, other compounds in the general formula of the present invention can be prepared by further following the preparation method of the above embodiment. A total of 5 compounds are synthesized, and the NMR data of the remaining compounds are as follows:

[0042] The NMR data result of A-2 is as follows: 11H NMR (500 MHz, Chloroform-d) δ 8.04 (dd, J = 1.6, 0.8 Hz, 1H), 7.17 (dd, J = 3.5, 0.7 Hz, 1H), 6.52 (dd, J = 3.5, 1.7 Hz, 1H), 5.80 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 4.98 (dd, J = 17.1, 2.0 Hz, 1H), 4.95 - 4.90 (m, 1H), 4.28 (t, J = 6.8 Hz, 2H), 2.06 - 2.01 (m, 2H), 1.76 - 1.73 (m, 2H), 1.38 (dq, J = 15.3, 5.1, 4.4 Hz 6H). 13 13C NMR (126 MHz, Chloroform-d) δ 157.26, 145.32, 144.60, 138.54, 118.57, 114.22, 110.95, 65.33, 33.54, 28.81 - 28.52 (m), 25.75

[0043] The 1H and 13C NMR data results of B-2 are as follows: 1 1H NMR (500 MHz, Chloroform-d) δ 7.56 (dd, J = 1.6, 0.7 Hz, 1H), 7.16 (dd, J = 3.5, 0.7 Hz, 1H), 6.49 (dd, J = 3.5, 1.7 Hz, 1H), 5.79 (ddt, J = 16.9, 10.2, 6.7 Hz, 1H), 4.99 (dq, J = 17.1, 1.6 Hz, 1H), 4.94 (ddd, J = 10.2, 2.0, 1.1 Hz, 1H), 4.29 (t, J = 6.8 Hz, 2H), 2.08 - 2.04 (m, 2H), 1.77 - 1.72 (m, 2H), 1.43 (dt, J = 6.8, 2.7 Hz, 4H). 13 13C NMR (126 MHz, Chloroform-d) δ 158.82, 146.17, 144.84, 138.65, 117.69, 114.51, 111.76, 64.98, 33.57, 28.52, 25.35.

[0044] The 1H and 13C NMR data results of B-3 are as follows: 1 1H NMR (600 MHz, Chloroform-d) δ 7.59 - 7.58 (m, 1H), 7.18 (d, J = 3.5 Hz, 1H), 6.51 (dd, J = 3.5, 1.7 Hz, 1H), 4.32 (t, J = 6.7 Hz, 2H), 2.22 - 2.18 (m, 2H). 13CNMR(151MHz, Chloroform-d) δ 158.8, 146.32, 144.88,

[0045] 137.42, 117.86, 115.52, 111.88, 64.44, 29.79.

[0046] Method for testing nematicidal activity:

[0047] 1. Preparation of liquid medicine

[0048] Dissolve the compound sample according to the received sample quality in a methanol solution containing 1% Tween-80 to prepare a stock solution for standby. During the experiment, gradient dilute the compound sample to prepare a 25 μg / mL liquid medicine. Water is used as the negative control, the commercial nematicide Lu Fuda and thiazoline are used as the positive controls, and 3-furoic acid is used as the control.

[0049] 2. Greenhouse test tube method

[0050] First, sterilize the sandy soil at high temperature. Take 5 mL of sandy soil in a 15 mL test tube, transplant the cucumber seedlings into the 15 mL test tube, add 1.6 mL of the liquid medicine to the experimental group, and set 5 replicates for each experiment. Cultivate in an artificial climate chamber at 26 °C for 4 weeks.

[0051] 3. Test results

[0052] The control results of 2-furoate derivatives against plant root-knot nematodes are shown in Table 3.

[0053] Table 3 Control effect (25 μg / mL, %)

[0054]

[0055] The control results of 3-furoate derivatives against plant root-knot nematodes are shown in Table 4.

[0056] Table 4 Control effect (25 μg / mL, %)

[0057]

[0058] In the present invention, the greenhouse test tube method was used to evaluate the in-vivo control effects of 2-furoic acid derivatives and 3-furoic acid derivatives against root-knot nematodes.

[0059] The results showed that the two synthesized 2-furoate derivatives could significantly inhibit the formation of cucumber root knots at a concentration of 25 μg / mL. Among them, the in-vivo control effect of compound A-2 against cucumber root-knot nematodes was comparable to that of the commercial nematicides Lu Fuda and thiazoline, and was superior to the 84% in-vivo control effect of the parent control 2-furoic acid at the same concentration; the relative root knot inhibition rate of A-1 was also 85%, showing a certain control effect, and no phytotoxicity was observed in cucumber seedlings at this concentration.

[0060] A total of three 3-furoate derivatives were synthesized in this study. Under the condition of a concentration of 25 μg / mL, the relative root-knot inhibition rate of Compound B-3 was 100%, which was comparable to that of the commercial nematicide Lu Fuda and other nematicides. The relative root-knot inhibition rate of Compound B-1 was 90%, which was better than that of the parent control 3-furoic acid (84%).

[0061] The results of activity-structure analysis showed that when R1 was the same, the relative root-knot inhibition rate of 3-furoate derivatives was higher than that of 2-furoate derivatives; when an F atom was introduced into the R1 substituent, the in-vivo nematicidal activity of the compound was significantly enhanced; in 3-furoate derivatives, when there was an alkynyl group in the R1 substituent, its relative root-knot inhibition rate was higher than that of the double-bond substituted derivative. The above results can provide new ideas for the design and synthesis of compounds with high nematicidal activity.

[0062] In summary, the compounds synthesized in this invention have good effects in controlling plant root-knot nematodes and can be used as lead compounds superior to the parent compounds for the research and development of new pesticides.

[0063] The above description of the disclosed embodiments enables those skilled in the art to implement or use the present invention. Various modifications to these embodiments will be obvious to those skilled in the art, and the general principles defined herein can be implemented in other embodiments without departing from the spirit or scope of the present invention. Therefore, the present invention will not be limited to the embodiments shown herein, but rather will be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. An ester compound containing a furan ring, characterized in that: Its structural formula is shown in formula (I) or (II): In the formula, R1 is selected from C5-C7 alkenyl, C3-C4 alkynyl, and trifluorobutenyl.

2. A furan ring-containing ester compound according to claim 1, characterized in that, R1 is selected from one of the following structures:

3. A method for preparing a furan ring-containing ester compound as claimed in claim 1, characterized in that: The ester compound containing furan ring represented by formula (I) or (II) is obtained by reacting 2-furancarboxylic acid or 3-furancarboxylic acid with halogenated olefin or halogenated alkyne compound.

4. The method for preparing the furan ring-containing ester compound according to claim 3, characterized in that: Using 2-furancarboxylic acid or 3-furancarboxylic acid and a halogenated olefin or halogenated alkyne compound as raw materials and tetrabutylammonium bromide as a catalyst, the reaction is refluxed at 80° C. in acetonitrile in the presence of potassium carbonate to obtain an ester compound containing a furan ring as shown in formula (I) (II).

5. The method for preparing the furan ring-containing ester compound according to claim 4, characterized in that: The molar ratio of 2-furancarboxylic acid or 3-furancarboxylic acid, halogenated olefin or halogenated alkyne compound, potassium carbonate and tetrabutylammonium bromide is 0.8-1.2: 1.2-1.8: 1.6-2.4: 0.13-0.

17.

6. Use of the furan ring-containing ester compound according to claim 1 in the preparation of an agricultural root-knot nematode killing preparation.

7. The use according to claim 6, characterized in that: The root-knot nematode is the southern root-knot nematode.

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