CN108484521A - The azilide compound and its preparation method and application of pesticide amido-containing acid ester or ureas structure - Google Patents

Abstract

The object of the present invention is to provide an azamacrolide compound containing a carbamate or urea structure for pesticides, a preparation method and its application as a fungicide and a quorum sensing regulator. The structure of this compound is shown in general formula (I): In the present invention, the azamacrolide compound containing a carbamate group and the azamacrolide compound containing a urea structure have better bactericidal and quorum sensing activities, and their activity is better than that of the parent, It can be used to prepare new pesticides.

Description

Azamacrolide compound containing carbamate or urea structure for pesticides and its Preparation method and use

technical field

The invention belongs to the field of organic synthesis for the creation of new pesticides, and specifically relates to an azamacrolide compound containing a carbamate or urea structure, a preparation method and an application thereof.

Background technique

A variety of known azamacrolide natural compounds have certain bactericidal and insecticidal activities, and a series of compounds derived from such natural products may also have insecticidal, acaricidal, bactericidal, herbicidal, Quorum sensing inhibition and other biological activities. At present, many related types of pesticide precursors are being researched and developed in the prior art, and a batch of pesticide varieties with good biological activity have also appeared, such as 13-aza-1,15-pentadecanolide compounds Mostly have better bactericidal activity (referring to Xiaolei Wang, European Journal of Medicinal Chemistry, 73 (2014) 286-294; Yanhong Dong, Green Chimstry, 2008,10,990-994; And the Chinese patent that the applicant of this application applies for earlier No. 200510085407.X "13-aza-1,15-pentadecanolactone, its preparation method and use as a fungicide" application date 2005.07.20), in recent years, this structure has been used as a parent for structural modification in order to obtain Compounds with better biological activity are currently the hotspot for the creation of new pesticides. However, the technical content of using this structure as the parent to prepare the azamacrolide compound containing carbamate or urea structure for pesticides has not been reported yet.

Contents of the invention

The object of the present invention is to provide an azamacrolide compound containing a carbamate or urea structure for pesticides, a preparation method thereof, and an application as a fungicide and a quorum sensing regulator.

To achieve the above object, the technical scheme of the present invention is as follows:

A kind of azamacrolide compound containing carbamate or urea structure for pesticide, it is characterized in that: the structure of this compound is as shown in general formula (I):

Wherein, n=1 or 5; when n=1, the compound of the general formula (I) is a 9-aza-1,11-undecalactone derivative; when n=5, the general formula ( I) The compound is a derivative of 13-aza-1,15-pentadecanolactone.

R is one of methoxy, propoxy, benzyloxy, OR ¹ , SR ² or NHR ³ , and the R ¹ , R ² and R ³ are substituted phenyl groups.

When the compound is a carbamate-containing azamacrolide compound, R is one of methoxy, propoxy, benzyloxy, OR ¹ or SR ² .

Wherein, R ^is phenyl, 2-chlorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-methylphenyl, 3,4-dichlorophenyl, 2-trifluoromethylbenzene One of base, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl or 2-(benzothiazol-2-yl)phenyl; R ² is benzothiazol-2-yl or 6 -Chlorobenzoxazol-2-yl.

When the compound is an azamacrolide compound containing a urea structure, R is NHR ³ .

Wherein, R ³ is one of 2-chlorophenyl, 4-chlorophenyl, 4-methylphenyl, 3,4-dichlorophenyl, 2-o-methoxyphenyl or 2-fluorophenyl kind.

The azamacrolide compound containing carbamate group is DN and DL series, and the azamacrolide compound containing urea structure is DN-A and DL-A series.

The compound is prepared by using 9-aza-1, 11-undecalactone compound or 13-aza-1, 15-pentadecanolactone compound as a precursor.

A preparation method of an azamacrolide compound containing a carbamate or urea structure for pesticides, the general reaction formula of the preparation method is:

.

Include at least the following steps:

1) Schmidt reaction of cyclooctanone (n=1) or cyclododecanone (n=5) with azidoethanol to obtain 9-aza-1,11-undecalactone (n=1) or 13 -Aza-1,15-undecalactone (n=5), the reaction formula is as follows,

2) The compound 9-aza-1,11-undecalactone or 13-aza-1,15-pentadecanolactone reacts with triphosgene to obtain 9-N-chloroformyl-9-aza-1, 11-undecalactone or 13-N-chloroformyl-13-aza-1,15-pentadecanolide, the reaction formula is as follows,

3) Compound 9-N-chloroformyl-9-aza-1,11-undecalactone or 13-N-chloroformyl-13-aza-1,15-pentadecanolactone with different alcohols , amine, and thiol compound react to obtain the azamacrolide compound of different substituents, and the reaction formula is as follows,

Wherein R is one of methoxy, propoxy, benzyloxy, OR ¹ , SR ² or NHR ³ .

Described R ^is phenyl, 2-chlorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-methylphenyl, 3,4-dichlorophenyl, 2-trifluoromethylbenzene One of base, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl or 2-(benzothiazol-2-yl)phenyl; R ² is benzothiazol-2-yl or 6 -Chlorobenzoxazol-2-yl; ^R3 is 2-chlorophenyl, 4-chlorophenyl, 4-methylphenyl, 3,4-dichlorophenyl, 2-o-methoxyphenyl Or one of 2-fluorophenyl.

In step 3), among the obtained azamacrolide compounds with different substituents, the substituents are respectively: carbamate, urea structure or thiocarbamate.

Use of the azamacrolide compound containing carbamate or urea structure for pesticides in the preparation of fungicides and quorum sensing regulators.

The bactericide is used to kill one or more of the following pathogens: tomato early blight, cucumber cinerea, apple rot, apple ringworm, wheat scab, and rapeseed sclerotinia.

The quorum sensing modulator is used in Agrobacterium tumefaciens.

The beneficial effect of the present invention is that: the present invention uses 13-aza-1,15-lactone fluoroborate (WLD) synthesized from natural macrolide compounds as the precursor, and derives and synthesizes a series of novel compounds, At the same time, the size of the ring was changed, and 12-ring azamacrolide derivatives were synthesized, and the biological activities of bactericidal and regulating quorum sensing were measured. Among them, the azamacrolide compounds (DN and DL series) containing carbamate groups and the azamacrolide compounds (DN-A and DL-A series) containing urea structure have certain bactericidal and quorum sensing activity, and its activity is superior to that of the parent. This provides a powerful reference for the creation of new pesticides in the future, and has the potential to continue research and development as new pesticides.

Description of drawings

Figure 1 is the proton nuclear magnetic resonance spectrum of compound DN-1 of the present invention.

Fig. 2 is the proton nuclear magnetic resonance spectrum of the compound DN-1A of the present invention.

Fig. 3 is the proton nuclear magnetic resonance spectrum of compound DL-1 of the present invention.

Figure 4 is the proton nuclear magnetic resonance spectrum of compound DL-1A.

Figure 5 is the proton nuclear magnetic resonance spectrum of compound DL-11.

Detailed ways

The specific implementation manners of the present invention will be further described in detail below in conjunction with the accompanying drawings and embodiments.

The general structural formula of the azamacrolide compound containing carbamate or urea structure of the present invention is shown in I:

Wherein, n=1 or 5; when n=1, the compound of general formula I is 9-aza-1,11-undecalactone derivatives (DL, DL-A series); when n=5 , the compound of general formula (I) is 13-aza-1,15-pentadecanolactone derivatives (DN, DN-A series).

Wherein, when R is one of methoxy, propoxy, benzyloxy, OR ¹ or SR ² , the compound is a carbamate-containing azamacrolide compound; when R is NHR ³ , the compound is an azamacrolide compound containing a urea structure.

Described R ^is phenyl, 2-chlorophenyl, 4-chlorophenyl, 4-nitrophenyl, 4-methylphenyl, 3,4-dichlorophenyl, 2-trifluoromethylbenzene one of 3-trifluoromethylphenyl, 4-trifluoromethylphenyl or 2-(benzothiazol-2-yl)phenyl. R ² is benzothiazol-2-yl or 6-chlorobenzoxazol-2-yl. R ³ is one of 2-chlorophenyl, 4-chlorophenyl, 4-methylphenyl, 3,4-dichlorophenyl, 2-o-methoxyphenyl or 2-fluorophenyl.

The preparation method of the azamacrolide compound containing carbamate or urea structure of the present invention comprises the steps:

1) Schmidt reaction of compound (II) or (III) with azide ethanol to obtain 9-aza-1,11-undecalactone (IV) or 13-aza-1,15-pentadecanolide (V);

2) Compound 9-aza-1,11-undecalactone (IV) or 13-aza-1,15-pentadecanolactone (V) reacts with triphosgene to obtain 9-N-chloroformyl-9 - aza-1,11-undecalactone (VI) or 13-N-chloroformyl-13-aza-1,15-pentadecanolactone (VII);

3) Compound (VI) reacts with different alcohols, amines, and thiol compounds to obtain compound (VIII);

4) compound (VII) reacts with different alcohols, amines, and thiol compounds to obtain compound (IX);

The general reaction formula is as follows:

Another object of the present invention is to provide the application of the azamacrolide compound containing carbamate or urea structure. The application provided by the present invention is the application of the azamacrolide compound containing carbamate or urea structure in the preparation of fungicides and quorum sensing regulators.

The bactericide is used to kill one or more of the following pathogens: tomato early blight, cucumber cinerea, apple rot, apple ringworm, wheat scab, and rapeseed sclerotinia.

The quorum sensing modulator is used in Agrobacterium tumefaciens.

1. Compound synthesis and related experimental data

a) Synthesis of 13-aza-1,15-pentadecanolactone (V)

(See "13-aza-1,15-pentadecanolactone, its preparation method and use as a fungicide" in Chinese Patent No. 200510085407.X "13-aza-1, 15-pentadecanolide" previously applied by the applicant, filing date 2005.07.20).

45.53g (0.25mol) of cyclododecanone was placed in the reaction flask, 100mL of dichloromethane was added to dissolve, and then 43.53g of azide ethanol was added. 143.43g (1.00mmol) 47% boron trifluoride ether solution was added dropwise, the dropwise addition was completed in 0.5h, refluxed for 10h, TLC detection (petroleum ether/ethyl acetate=10:1(v/v)) cyclododecanone After the reaction was completed, 500 mL of saturated aqueous sodium bicarbonate solution was added dropwise, reacted at room temperature for 30 h, extracted the reaction liquid with dichloromethane (200 mL×5), dried over anhydrous sodium sulfate, filtered off the desiccant, and evaporated to obtain a reddish-brown viscous solution. Thick liquid 69.91g, yield 85%.

b) Synthesis of 13-N-formyl chloride-13-aza-1,15-pentadecanolide (VII)

At room temperature, take 12.29 g (41.43 mmol) of triphosgene (BTC) and add it to a 250 ml three-necked reaction flask, draw 100 ml of tetrahydrofuran (THF) into the reaction device with a syringe, and stir to dissolve triphosgene. Take 5ml of triethylamine and add it to the dropping funnel and drop it into the reaction flask. After 10 minutes, add the 13-aza-1,15-pentadecanolactone obtained in the step a) of dissolving tetrahydrofuran into the dropping funnel, and add it dropwise into the reaction bottle, and detect it by thin layer chromatography (TLC) 5 hours after the addition is completed. (Petroleum ether/ethyl acetate=10:1 (V/V)) The reaction of raw materials was completed. 100 ml of deionized water was added dropwise to the reaction system in an ice bath to quench the reaction. The reaction solution was extracted with dichloromethane (3×50ml), washed with saturated sodium chloride (2×100ml), washed with deionized water (2×100ml), dried over anhydrous magnesium sulfate, and filtered to remove the solvent to obtain 25g of light yellow viscous liquid. The product was chromatographed on silica gel (200-300 mesh) (petroleum ether/ethyl acetate=25/1 (V/V)) to obtain 24 g of a colorless transparent liquid, which was 13-N-formyl chloride-13-aza -1,15-pentadecanolactone, the yield is 95%.

c) Synthesis of 9-aza-1,11-undecalactone (IV)

12.71g (0.1mol) of cyclooctanone and 10.62g (0.12mol) of ethanol azide were dissolved in 80mL of dichloromethane, and 36.26g (0.26mol) of 47% boron trifluoride ether was added dropwise, and the addition was completed within 3 hours. Heat to reflux for 20 hours after rising to room temperature, thin layer chromatography (TLC) detection (petroleum ether/ethyl acetate=10:1 (v/v)) cyclooctanone reaction is complete, add 300mL saturated sodium bicarbonate solution dropwise, stir at room temperature Overnight, extracted with dichloromethane (60mL×6), combined the organic layers, dried over anhydrous sodium sulfate, filtered off the desiccant, and rotary evaporated to obtain 17g of yellow viscous liquid with a yield of 92%.

d) Synthesis of 9-N-chloroformyl-9-aza-1,11-undecalactone (VI)

At room temperature, take 16.82g (0.057mol) of triphosgene (BTC) and add it to a 250mL three-necked reaction flask, draw 100ml of tetrahydrofuran (THF) into the reaction device with a syringe, and stir to dissolve triphosgene. Take 7mL of triethylamine and add it to the dropping funnel and drop it into the reaction flask. After 10 minutes, add the 9-aza-1,11-undecalactone obtained in step c) of dissolving tetrahydrofuran into the dropping funnel, and add it dropwise into the reaction bottle, and detect it by thin layer chromatography (TLC) 5 hours after the addition is completed. (Petroleum ether/ethyl acetate=15:1 (V/V)) The reaction of raw materials was completed. 100 mL of deionized water was added dropwise to the reaction system in an ice bath to quench the reaction. The reaction solution was extracted with dichloromethane (3×50mL), washed with saturated sodium chloride (2×100mL), washed with deionized water (2×100mL), dried over anhydrous magnesium sulfate, and filtered to remove the solvent to obtain 26.02 g of light yellow viscous thick liquid. The product was chromatographed on silica gel (200-300 mesh) (petroleum ether/ethyl acetate=25/1 (V/V)) to obtain 24 g of a colorless transparent liquid, namely 9-N-chloroformyl-9-aza -1,11-undecalactone, the yield is 91%.

e) Preparation of carbamate-containing azamacrolide compounds (taking DL-1 as an example)

Dissolve 1g (4.04mmol) of 9-N-chloroformyl-9-aza-1,11-undecalactone, 0.63g (4.84mmol) of p-chlorophenol and 0.558g (4.04mmol) of potassium carbonate at room temperature 15mL of anhydrous acetonitrile, and then heated to reflux for 5h. The reaction solution was cooled to room temperature and desolvated. The residue was dissolved in 20 mL of water and extracted with dichloromethane (2×20 mL). The organic phases were combined, washed with 2% potassium carbonate aqueous solution and water, and dried over anhydrous sodium sulfate. Precipitation by filtration, the residue was separated by silica gel (200-300 mesh) chromatography (petroleum ether/ethyl acetate=10:1 (V/V)), and 1.15 g of light yellow liquid was obtained, which was DL-1. The yield 84%.

Structural Confirmation Data:

¹ H NMR (300MHz, CDCl ₃ ): δ7.35–7.27(m,2H),7.05(d,J=8.7 Hz,2H),4.50–4.27(m,2H),3.80–3.59(m,2H) ,3.53–3.32(m,2H), 2.49–2.35(m,2H),1.71(dt,J＝10.7,4.5Hz,4H),1.43(s,6H).

f) Preparation of azamacrolide compounds containing urea structure (taking DL-1A as an example)

0.52g (4.04mmol) of p-chloroaniline, 0.49g (4.04mmol) of DMAP and 15mL of anhydrous dichloromethane were successively added into a 100mL round bottom flask. Dissolve 1g (4.04mmol) of 9-N-chloroformyl-9-aza-1,11-undecalactone and 0.67mL of triethylamine in 10mL of anhydrous dichloromethane, and add dropwise to in the flask. After the dropwise addition was completed, it was slowly raised to room temperature and stirred overnight. TLC monitoring (petroleum ether/ethyl acetate=3:1 (V/V)) until the reaction of the raw materials is complete, the reaction mixture is diluted with 30 mL of water, extracted with dichloromethane (2×20 mL), the organic phases are combined, and washed with saturated chloride Washed with sodium solution and dried over anhydrous sodium sulfate. Precipitation by filtration, the residue was separated by silica gel (200-300 mesh) chromatography (petroleum ether/ethyl acetate=10:1 (V/V)), and 0.7 g of a khaki solid was obtained, which was DL-1A with a melting point of 108 -110°C, yield 50%.

Structural Confirmation Data:

¹ H NMR (300MHz, CDCl ₃ ): δ7.33–7.27(m,2H),7.25–7.18(m,2H),6.49(s,1H),4.37–4.23(m,2H),3.74–3.59( m,2H),3.35(t,J=7.2 Hz,2H),2.48–2.34(m,2H),1.78–1.57(m,4H),1.56–1.31(m,6H).

g) Preparation of azamacrolide compounds containing thiocarbamate (taking DN-11 as an example)

0.3g (1.81mmol) 2-mercaptobenzothiazole, 0.08g (0.66mmol) DMAP, 0.28mL (1.98mmol) triethylamine and 15mL anhydrous dichloromethane were successively added into a 100mL round bottom flask. 0.5 g (1.65 mmol) of 13-N-chloroformyl-13-aza-1,15-undecalactone obtained in step b) dissolved in 10 mL of anhydrous dichloromethane was added dropwise with stirring in an ice bath. After the dropwise addition was completed, it was slowly raised to room temperature and stirred overnight. The reaction solution was diluted with 30 mL of water, extracted with dichloromethane (2×20 mL), and the organic phases were combined, washed with 2% potassium carbonate aqueous solution and water, and dried over anhydrous sodium sulfate. Precipitation by filtration, the residue was separated by silica gel (200-300 mesh) chromatography (petroleum ether/ethyl acetate=10:1 (V/V)) to obtain 0.34 g of a white solid with a melting point of 75-77°C and a yield of 46 %.

Structural Confirmation Data:

¹ H NMR (300MHz, CDCl ₃ ): δ8.04–7.97(m,1H),7.89(d,J=7.8 Hz,1H),7.51–7.36(m,2H),4.36(t,J=4.8Hz ,2H),3.72(t,J＝4.9Hz, 2H),3.50(s,2H),2.38(t,J＝7.0Hz,2H),1.70(dd,J＝13.7,6.8Hz,4H), 1.48 –1.27(m,14H).

The compounds of each embodiment (DN series, DN-A series, DL series, DL-A series) of the present invention were prepared according to the above method. The compound number, molecular formula, structural formula, appearance, melting point and yield data of the examples are shown in Table 1; NMR and high-resolution mass spectrometry data are shown in Table 2.

2. Determination of biological activity

1. Determine the inhibitory activity of the target compound on the mycelial growth rate of six plant pathogenic bacteria, so as to find a lead compound with better activity for subsequent optimization. The specific experimental process and results are as follows.

a.Experimental material

Control reagents: fludioxonil, carbendazim, the measured concentration is 50mg/L. Test agent: target compound (total 42)

The tested pathogenic fungi were preserved for a long time in the laboratory of Teacher Yan Xiaojing from the Institute of Plant Protection, Academy of Agricultural Sciences, and then they were multiplied for later use. The assay concentration of bactericidal activity is 50mg/L.

The target of the test: tomato early blight fungus Alternaria solani Deuteromycotina, Hyphospora, Alternaria genus, widely distributed, the host plant is tomato.

Cucumber gray mold Botrytis cinerea Deuteromycotina, Hyphomycetes, Botrytis, Botrytis cinerea.

Apple rot pathogen Valsa mali Deuteromycetes, Coelomyces, Ascospora.

Apple ring spot Macrophoma kuwatsukai Ascomycetes, Botrytis spp., called ring spot bacteria. Widely distributed, host plants include: apple, pear, peach, plum, apricot, hawthorn, etc.

Wheat head blight fungus Gibberella zeae Deuteromycotina, Hyphomycetes, Fusarium graminearum Fusarium.

Rapeseed Sclerotinia Sclerotinia sclerotiorum Fungi Ascomycota, Mollicolales, Sclerotinia, Sclerotinia. Distributed in the Yangtze River Basin, South China Coast, and Southwest China, the host plants include cruciferous and solanaceous vegetables, peanuts, soybeans, cucumbers, sunflowers, onions, citrus and other plants.

b. Experimental method

Bactericidal test method: the test agent was prepared with DMSO into a 30000mg/L solvent, and then diluted 600 times with PDA medium to make a toxic medium; the control solvent DMSO was diluted 600 times with the medium to make a culture medium containing DMSO Base (final concentration 50mg/L). According to the Agricultural Industry Standard of the People's Republic of China (NY/T1156.2-2006), the cultured pathogenic bacteria were aseptically operated under aseptic conditions with a 7mm diameter sterile puncher to obtain the bacteria cake from the edge of the colony, and the sterilized inoculation needle Inoculate the fungus cake in the center of the toxic medium plate, cover the dish with the mycelium facing down, and place it upside down in a 25°C incubator for cultivation. Investigate the growth of mycelia of pathogenic bacteria according to the growth of mycelium in the blank control petri dish. After the mycelium in the blank control has fully grown, measure the colony diameter (mm) with the cross method, and take the average value. The diameter of the colony - the diameter of the bacterial cake = The expanded diameter of the plate. According to the formula (1), the cell growth inhibition rate was calculated.

2. The quorum sensing activity of the target compound against Agrobacterium tumefaciens was determined by the β-galactosidase activity method.

See Table 3 and Table 4 for biological activity assay results.

As can be seen from Table 1, adopt the preparation method of the azamacrolide compound containing carbamate or urea structure of the present invention to prepare the product containing carbamate or urea structure azamacrolide compound The rate is 40-97%.

It can be seen from Table 3 and Table 4 that the azamacrolide compound containing carbamate or urea structure of the present invention has good bactericidal and quorum sensing regulating effects. The results in Table 3 show that compounds such as DN-FA, DL-1A, DL-9, DL-10, DL-14A, DL-13, and DN-14A have inhibitory effects on more than three of the six pathogenic bacteria. The bactericidal activity of the aza twelve-membered ring macrolide series compound is better than that of the sixteen-membered ring lactone compound. Table 4 result shows that compounds such as DN-3A, DN-6A, DN-10A, DN-10, 16GD-D have certain quorum sensing inhibitory activity to Agrobacterium tumefaciens; And DL-0, DL-11, DL-12 , DL-13, DL-10A, DL-5A, DN-14A and other compounds have certain quorum sensing promotion activities. The quorum sensing inhibitory activity of 16-membered ring compounds is better than that of 12-membered ring compounds.

The experimental data of the compound of each embodiment of table 1

¹ H-NMR and high resolution mass spectrometry data of the compound of each embodiment of table 2

The compound of each embodiment of table 3 is to phytopathogenic mycelia growth inhibitory rate

The compound of each embodiment of table 4 is to the quorum sensing activity assay result of Agrobacterium tumefaciens

Claims (9)

1. the azilide compound of a kind of pesticide amido-containing acid ester or ureas structure, it is characterised in that：The chemical combination The structure of object is as shown in logical formula (I)：

Wherein, n=1 or 5；As n=1, the logical formula (I) compound is 9- azepine -1,11- undecalactone derivatives；Work as n= When 5, the logical formula (I) compound is 13- azepine -1,15- pentadecanolides derivatives；

R is methoxyl group, propoxyl group, benzyloxy, OR¹、SR²Or NHR³In one kind, the R¹、R²、R³For substituted-phenyl.

2. azilide compound as described in claim 1, it is characterised in that：

When the compound is the azilide compound of amido-containing acid ester, R is methoxyl group, propoxyl group, benzyloxy, OR¹Or SR²In one kind；

Wherein, R¹For phenyl, 2- chlorphenyls, 4- chlorphenyls, 4- nitrobenzophenones, 4- aminomethyl phenyls, 3,4- dichlorophenyls, 2- trifluoros One kind in aminomethyl phenyl, 3- trifluoromethyls, 4- trifluoromethyls or 2- (benzothiazole -2- bases) phenyl；R²For benzene And thiazol-2-yl or 6- Lv benzoxazole -2- bases.

3. azilide compound as described in claim 1, it is characterised in that：

When the compound is the azilide compound of the structure containing ureas, R NHR³；

Wherein, R³For 2- chlorphenyls, 4- chlorphenyls, 4- aminomethyl phenyls, 3,4- dichlorophenyls, 2- o-methoxyphenyls or 2- fluorobenzene One kind in base.

4. the azilide compound as described in one of claim 2-3, it is characterised in that：

The azilide compound of the acid esters containing urethane groups is DN and DL series, the azepine of the structure containing ureas Macrocyclic lactone compounds are DN-A and DL-A series.

5. azilide compound as claimed in claim 2, it is characterised in that：

The compound use 9- azepine -1,11- undecalactone class compounds or 13- azl, 15-pentadecanolide class compounds for It is prepared by parent.

6. a kind of pesticide amido-containing acid ester of one of such as Claims 1 to 4 or the azilide chemical combination of ureas structure The preparation method of object, it is characterised in that：The reaction formula of the preparation method is：

。

7. preparation method as claimed in claim 6, it is characterised in that：Including at least following steps：

1) cyclooctanone (n=1) or cyclododecanone (n=5) are carried out Schmidt with nitrine ethyl alcohol to react, obtain azepine -1 9-, 11- undecalactones (n=1) or 13- azepines -1,15- undecalactone (n=5), reaction equation is as follows,

2) 9-N- chlorine is obtained by the reaction with triphosgene in compound 9- azepines -1,11- undecalactones or 13- azl, 15-pentadecanolides Formoxyl -9- azepines -1,11- undecalactone or 13-N- chloroformyl -13- azepine -1,15- omega-pentadecanolides, reaction equation is as follows,

3) compound 9-N- chloroformyls -9- azepine -1,11- undecalactones or 13-N- chloroformyl -13- azepines -1,15- ten The azilide compound of different substituents is obtained by the reaction from different alcohol, amine, mercaptan compound for five lactones, and reaction equation is such as Under,

Wherein R is methoxyl group, propoxyl group, benzyloxy, OR¹、SR²Or NHR³In one kind；

The R¹For phenyl, 2- chlorphenyls, 4- chlorphenyls, 4- nitrobenzophenones, 4- aminomethyl phenyls, 3,4- dichlorophenyls, 2- fluoroforms One kind in base phenyl, 3- trifluoromethyls, 4- trifluoromethyls or 2- (benzothiazole -2- bases) phenyl；R²For benzo Thiazol-2-yl or 6- Lv benzoxazole -2- bases；R³For 2- chlorphenyls, 4- chlorphenyls, 4- aminomethyl phenyls, 3,4- dichlorophenyls, 2- One kind in o-methoxyphenyl or 2- fluorophenyls.

8. preparation method as claimed in claim 7, it is characterised in that：

In step 3), in the azilide compound of obtained different substituents, the substituent group is respectively：Amino first Acid esters, ureas structure or thiocarbamate.

9. prepared by the azilide compound of pesticide amido-containing acid ester as described in claim 1 or ureas structure Purposes in fungicide, quorum sensing conditioning agent, it is characterised in that：

The fungicide is for killing following one or more germs：Tomato early blight bacterium, botrytis cinerea pers, canker of apple fruit Bacterium, Botryosphaeria berengeriana f. sp, fusarium graminearum, Sclerotinia sclerotiorum；

The quorum sensing conditioning agent is used for Agrobacterium tumefaciens.