CN107721956A - Benzo butyrolactone derivative, synthetic method and its application for preparing bactericide - Google Patents
Benzo butyrolactone derivative, synthetic method and its application for preparing bactericide Download PDFInfo
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Abstract
The invention discloses benzo butyrolactone derivative, synthetic method and its application for preparing bactericide, using Sesquiterpene lactones pharmacophore α methylene gamma butyrolactone as lead compound, integrate benzofuranone pharmacophore, modified in its α methylene base location, orient derivative synthesis and go out a series of α alkenylenes benzo butyrolactone compounds, and the bacteriostatic activity of this kind of compound is determined, the high-activity compound of 2 tool Developing Prospects on Industrialized Exploitation has been synthesized on the basis of this structure effect.For preventing and treating the plant diseases caused by pathogen such as wheat powdery mildew, wheat scab, take-all, wheat sharp eyespot, the leaf blight of corn, rice sheath blight disease, rice blast, cotton seedling blight, Phytophthora capsici disease, graw mold of tomato, leaf muld of tomato, tomato morning late blight, cucumber anthracnose, cucumber fusarium axysporum, sclerotinia sclerotiorum.
Description
Technical field
The invention belongs to chemistry noval chemical compound field, and in particular to benzo butyrolactone derivative, synthetic method and its
Prepare the application of bactericide.
Background technology
Find efficient, low toxicity, the biogenic pesticide of low-residual is current one of focus of Pesticide Science area research both at home and abroad.
Alpha-methylene-gamma-butyrolactone is the main pharmacodynamics group of Sesquiterpene lactones compound, during our early-stage Studies, α-Asia
Methyl-gamma-butyrolactone class compound has preferable bacteriostatic activity, and benzofuranones have antibacterial, anti-mistake
Quick, AntiHIV1 RT activity and the multiple pharmacological effect such as antitumor.Therefore the present invention integrates both pharmacophores, enters in its alpha-methylene position
Row modification, orientation derivative synthesis go out a series of α-alkenylene benzo butyrolactone compound, and base is identified for exploitation high activity bactericide
Plinth.
The content of the invention
The present invention relates to a kind of bactericidal benzo butyrolactone derivative, particularly, two obtained on this basis
The high-activity compound of kind tool Developing Prospects on Industrialized Exploitation and its application as bactericide in terms of controlling plant diseases.This hair
Bright purpose is to provide a kind of bactericidal benzo butyrolactone derivative as bactericide in controlling plant diseases side
Using.
In order to realize above-mentioned task, the present invention takes following technical solution：
Benzo butyrolactone derivative, shown in the general structure such as formula (one) of the analog derivative：
R group be selected from monosubstituted phenyl, disubstituted aryl, the direct-connected alkyl of saturation, heterocyclic aryl containing S, heterocyclic aryl containing N,
One kind in heterocyclic aryl containing O and polyaromatic.
Specifically, the structure of R group is as shown in table 1：
Table 1
The synthetic method of benzo butyrolactone derivative, including be by the mol ratio of o-hydroxy phenylacetic acid and p-methyl benzenesulfonic acid
10:Backflow 4h obtains benzofuranone at 120~130 DEG C after 1 mixing；The mol ratio of benzofuranone and substituted benzaldehyde
For 1:10ml triethylamines and 15ml the acetic anhydrides 12h that flowed back at 80 DEG C, which are added, after 2 mixing obtains reaction product, reaction product
Benzo butyrolactone derivative is produced after abstraction purification.
Further, including the compound of formula (two) and formula (three)：
Described formula (two) and the preparation method of the compound of formula (three) include：
After being mixed to R septichens 50mmol, sulphur powder 100mmol and p-methyl benzenesulfonic acid 1.75mmol 120~
Flow back 8h at 130 DEG C, adds sodium hydrate aqueous solution 10ml and the mmol of four butyl bromation amine 1.25 that mass concentration is 20%
The hydrolysis 8h at 100 DEG C, regulation pH obtain 3-R o-hydroxy phenylacetic acids for 7；
5mmol 3-R o-hydroxy phenylacetic acids stir 16h with 15mL phosphorus oxychlorides in 50mL dichloromethane, obtained production
Thing obtains 3-R benzofuranones through washing and drying after purification；
1.5mmol 3-R benzofuranones and 3mmol that 10mL is added in the environment that pH is 8 to trifluro benzaldehyde is dense
Spending for 10mol/L potassium hydroxide-ethanol solutions and the crude product that 14h obtains is stirred at room temperature, the pH for adjusting crude product is 7,
Again by crude product successively through extracting, washing, drying and obtaining after purification to trifluoromethylbenzene (3-R) benzo butyrolactone；
R is fluorine or triazole.
Described benzo butyrolactone derivative is used for the application for preparing bactericide.
Described benzo butyrolactone derivative can be used for preparing preventing and treating plant disease as caused by plant pathogenic fungi
Pesticidal preparations.
The microbial plant disease of described phytonosis includes：Wheat powdery mildew, wheat scab, take-all,
Wheat sharp eyespot, the leaf blight of corn, rice sheath blight disease, rice blast, cotton seedling blight, Phytophthora capsici disease, tomato gray mould
Disease, leaf muld of tomato, tomato morning late blight, cucumber anthracnose, cucumber fusarium axysporum and sclerotinia sclerotiorum.
The form of described pesticidal preparations includes wettable powder, missible oil, microemulsion, soluble liquid, aqua, moisture
Shot agent, aqueous emulsion, granule and suspending agent.
Compound wettable powder, breast is made with Bravo or other commercialization fungicide compoundings in described pesticidal preparations
Oil, microemulsion, soluble liquid, aqua, water dispersible granules, aqueous emulsion, granule or suspending agent.
Advantages of the present invention includes：
The bactericidal benzo butyrolactone derivative of the present invention has the strong bactericidal activity more composed, its α-sub- alkene
Base bit substituent electronegativity power has material impact to the bactericidal activity of such compound, transform alpha-methylene as α-Asia
Alkenyl, a series of derivatives are generated, the bactericidal activity of gained compound increases, and changes when on benzo butyrolactone phenyl ring
When making as with fluoro-containing group and bactericidal triazole group, bactericidal activity greatly improves.
Brief description of the drawings
Fig. 1 is compound 4- fluorophenyl benzo butyrolactone1H NMR spectras；
Fig. 2 is compound 4- fluorophenyl benzo butyrolactone13C NMR spectras；
Fig. 3 is HR-MS (ESI) collection of illustrative plates of compound 4- fluorophenyl benzo butyrolactone；
Fig. 4 is compound 2- pyridine benzo butyrolactone1H NMR spectras；
Fig. 5 is compound 2- pyridine benzo butyrolactone13C NMR spectras；
Fig. 6 is HR-MS (ESI) collection of illustrative plates of compound 2- pyridine benzo butyrolactone；
The present invention is illustrated below in conjunction with specification drawings and specific embodiments.
Embodiment
Using pharmacophore alpha-methylene-gamma-butyrolactone as lead compound, one is synthesized with backbone integration strategy using pharmacophore
Serial benzo butyrolactone compound, using botrytis cinerea and cucumber anthracnose as trying bacterium determination bacteriostatic activity, lead to
Cross Structure-activity analysis, thus it is speculated that the ideal structure of high-activity compound, and the height for having synthesized 2 tool Developing Prospects on Industrialized Exploitation is living
Property compound.
Bactericidal benzo butyrolactone derivative, shown in the general structure such as formula (one) of the analog derivative, eachization
Compound title and substituted radical (R group) structure are as shown in table 1.
Table 1
The synthesis of benzo butyrolactone derivative:
Benzo butyrolactone derivative is synthesized by following route：
I.e.：O-hydroxy phenylacetic acid 3g (19.7mmol) is taken, p-methyl benzenesulfonic acid 1.75mmol, is flowed back at 120~130 DEG C
4h, benzofuranone crude product is obtained, the silica gel column chromatography technology for choosing petrol ether/ethyl acetate system is divided product
From purifying.Benzofuranone 1.5mmol, substituted benzaldehyde 3mmol, 10ml triethylamine, 15ml acetic anhydrides are added round bottom and burnt again
In bottle, flow back 12h at 80 DEG C.Product is spin-dried for by TLC tracking and monitorings to after the completion of reacting under vacuum condition, ethyl acetate extraction
Three times, collect ethyl acetate phase to be stayed overnight with anhydrous sodium sulfate drying, vacuum is spin-dried for product.
According to reacting coarse product polarity size from petroleum ether/dichloromethane, petrol ether/ethyl acetate, petroleum ether/the third
A certain expansion system in ketone, petroleum ether/dichloromethane/ethyl acetate, adjust to appropriate proportioning, integrated use recrystallization, silicon
Plastic column chromatography, prepare the technologies such as thin-layer chromatography and separated, purified, respectively obtain a series of benzo butyrolactone derivative,
The benzo butyrolactone derivative for carrying different R groups is finally given according to the different substituted benzaldehydes of addition.
Purge process is illustrated by phenyl of substituent R：Obtained crude product phenyl benzo butyrolactone is used into body respectively
Product is than being 10:Three kinds of 1 petroleum ether/dichloromethane, petrol ether/ethyl acetate and petroleum ether/acetone dicyandiamide solutions are in thin layer
To deploy on analysis plate, wherein two kinds of systems of petroleum ether/dichloromethane and petroleum ether/acetone can not separate product and magazine spot,
And petrol ether/ethyl acetate dicyandiamide solution then makes product point and impure point completely separable, therefore select petrol ether/ethyl acetate
Solvent is as silica gel column chromatography eluant, eluent.Column chromatography is using wet method dress post, loading, gradient elution, eluant, eluent：Petroleum ether：Acetic acid
Ethyl ester (V/V)=20:1→10:1, TLC tracking and monitoring product, Rotary Evaporators are concentrated under reduced pressure the eluant, eluent of collection,
Obtain final product (yield 90%, purity 90%).To obtain the higher compound of purity, the product utilization petroleum ether that will obtain：
Ethyl acetate solvent system is recrystallized, and picking 1g or so products are put into 100mL beakers, and it is molten to add 10mL ethyl acetate
Liquid is completely dissolved it, then adds 80mL or so petroleum ether and stirs, and beaker is placed on into ventilation hangs 2d or so directly
Separated out to yellow crystals in walls of beaker, medication spoon gently scrapes, and can obtain the end-product phenyl benzo fourth of purity more than 99%
Lactone, ultimate yield is 80% or so.Other compounds can be purified according to the method described above.
2nd, the synthesis of benzo butyrolactone derivative is substituted:
The benzo butyrolactone derivative of the present invention also includes the compound of formula (two) and formula (three)；
Benzo butyrolactone derivative is substituted to be synthesized by following route：
I.e.：Take to R septichen 50mmol, sulphur powder 100mmol, p-methyl benzenesulfonic acid 1.75mmol, 120~130
Flowed back 8 hours at DEG C, TLC tracking and monitorings add the sodium hydrate aqueous solution that mass concentration is 20% to after the completion of reacting
10ml and four butyl bromation amine 1.25mmol, the hydrolysis 8h at 100 DEG C, and obtain crude product A with hydrochloric acid regulation pH=7
(3-R o-hydroxy phenylacetic acids).5mmol crude products A stirs 16h with 15mL phosphorus oxychlorides in 50mL dichloromethane, obtained production
Thing is dried overnight after being washed respectively with dichloromethane, water, chooses the silica gel column chromatography technology pair of petrol ether/ethyl acetate system
Obtained product is isolated and purified to obtain product B (3-R benzofuranones).1.5 mmol product B and 3mmol to trifluoro
Benzaldehyde adds 10mL concentration in the environment that pH is 8 and is 10mol/L potassium hydroxide-ethanol solutions and 14h is stirred at room temperature,
Obtained crude product salt acid for adjusting pH is 7, is washed after ethyl acetate extraction with water, bittern (saturated nacl aqueous solution).It is anhydrous
Sodium sulphate chooses petrol ether/ethyl acetate system silica gel column chromatography technology after being dried overnight to product isolate and purify
To final product C (to trifluoromethylbenzene (3-R) benzo butyrolactone), R is fluorine atom or triazole group.
3. the physicochemical property and spectral data of compound
Phenyl benzo butyrolactone：Yield 80%, yellow crystals；mp:116.1-117.3℃；1H NMR(500MHz,
CDCl3) δ 8.19 (dd, J=6.5,2.9Hz, 2H), 7.63 (s, 1H), 7.55 (d, J=7.6Hz, 1H), 7.51-7.47 (m,
3H), 7.37-7.31 (m, 1H), 7.19 (t, J=7.6Hz, 1H), 7.11 (d, J=8.0Hz, 1H)13C NMR(126MHz,
CDCl3):δ165.90,153.05,140.35,133.17,132.02, 131.19,129.91,128.75,125.42,
123.75,120.84,119.45,111.06.HR-MS(ESI): m/z calcd for C15H10O2([M+Na]+)
222.0681,found 245.0573.
2- chlorphenyl benzo butyrolactone：Yield 86%, yellow crystals；mp:128.3-129.1℃；1H NMR(500 MHz,
CDCl3) δ 7.92 (s, 1H), 7.75 (dd, J=7.5,1.6Hz, 1H), 7.54-7.50 (m, 1H), 7.46-7.42 (m, 2H),
7.40-7.36 (m, 1H), 7.34 (ddd, J=8.7,5.5,1.2Hz, 1H), 7.12 (d, J=8.1Hz, 1H), 7.00 (td, J
=7.7,0.9Hz, 1H)13C NMR(126MHz,CDCl3): δ168.20,154.67,137.05,135.73,135.18,
134.65,132.55,131.60,131.43, 129.79,126.83,122.98,121.47,120.23,111.31.HR-MS
(ESI):m/z calcd for C15H9ClO2([M+H]+)256.0291,found 257.0364.
3- chlorphenyl benzo butyrolactone：Yield 82%, yellow crystals；mp:131.2-132.2℃；1H NMR(500MHz,
CDCl3) δ 8.17 (s, 1H), 8.08 (d, J=7.2Hz, 1H), 7.55 (d, J=6.0Hz, 2H), 7.45-7.40 (m, 2H),
7.39-7.35 (m, 1H), 7.20 (t, J=7.4Hz, 1H), 7.13 (d, J=8.0Hz, 1H)13C NMR(126MHz,
CDCl3):δ 166.10,153.34,138.07,134.73,134.53,131.47,131.05,130.46,129.81,
129.76,124.97,123.93,122.88,119.64,111.21.HR-MS(ESI): m/z calcd for C15H9ClO2
([M+H]+)256.0291,found 257.0364.
4- chlorphenyl benzo butyrolactone：Yield 84%, yellow crystals；mp:127.4-128.7℃；1H NMR(500MHz,
CDCl3) δ 8.15 (d, J=8.6Hz, 2H), 7.58-7.53 (m, 2H), 7.45 (d, J=8.6Hz, 2H), 7.36 (td, J=
7.9,1.1Hz, 1H), 7.22-7.17 (m, 1H), 7.12 (d, J=8.0Hz, 1H)13C NMR(126MHz,CDCl3):δ
165.88,153.14,138.57,137.41,133.26,131.61,130.94, 130.19,128.91,125.18,
123.91,121.37,119.49,110.95,101.04.HR-MS(ESI): m/z calcd for C15H9ClO2([M+H]+)
256.0291,found 257.0364.
2- bromophenyl benzo butyrolactone：Yield 88%, yellow crystals；mp:148.8-149.7℃；1H NMR(500 MHz,
CDCl3) δ 8.19 (dd, J=7.8,1.2Hz, 1H), 7.89 (d, J=4.0Hz, 1H), 7.67 (d, J=8.0Hz, 1H), 7.62
(d, J=7.6Hz, 1H), 7.41 (t, J=6.5Hz, 1H), 7.38-7.34 (m, 1H), 7.33-7.28 (m, 1H), 7.22 (t, J
=7.6Hz, 1H), 7.13 (t, J=6.5Hz, 1H)13C NMR(126MHz,CDCl3):δ166.52,153.37,138.67,
138.20,132.75,132.12,131.89, 130.64,129.87,127.25,125.42,124.56,123.89,
120.23,111.03.HR-MS(ESI): m/z calcd for C15H9BrO2([M+Na]+)299.9786,found
322.9678.
3- bromophenyl benzo butyrolactone：Yield 79%, yellow solid；mp:149.6-150.4℃；1H NMR(500MHz,
CDCl3) δ 8.29 (s, 1H), 8.15 (d, J=7.9Hz, 1H), 7.60 (d, J=9.5Hz, 1H), 7.55 (d, J=10.0Hz,
2H), 7.40-7.34 (m, 2H), 7.20 (t, J=7.6Hz, 1H), 7.13 (d, J=8.1Hz, 1H)13C NMR(126MHz,
CDCl3):δ166.84,154.13,138.02,135.40,134.42, 133.96,130.49,130.22,130.05,
128.00,125.22,123.96,122.73,119.66,111.02. HR-MS(ESI):m/z calcd for C15H9BrO2
([M+Na]+)299.9786,found 322.9678.
4- bromophenyl benzo butyrolactone：Yield 88%, yellow solid；mp:142.1-143.2℃；1H NMR(500MHz,
CDCl3) δ 8.07 (d, J=8.5Hz, 2H), 7.63-7.58 (m, 2H), 7.55 (d, J=6.3Hz, 2H), 7.36 (td, J=
7.9,1.2Hz, 1H), 7.19 (td, J=7.6,0.8Hz, 1H), 7.12 (d, J=8.0Hz, 1H)13C NMR(126MHz,
CDCl3):δ166.50,153.15,138.62,133.35,132.00, 131.89,130.24,126.02,125.17,
123.93,122.44,119.52,110.97.HR-MS(ESI): m/z calcd for C15H9BrO2([M+Na]+)
299.9786,found 322.9678.
2- fluorophenyl benzo butyrolactone：Yield 83%, yellow solid；mp:135.1-135.3℃；1H NMR(500MHz,
CDCl3) δ 8.22 (m, 1H), 8.14 (s, 1H), 7.59 (s, 1H), 7.56 (d, J=7.7Hz, 1H), 7.36 (m, 1H), 7.22
(d, J=7.9Hz, 1H), 7.16 (d, J=2.3Hz, 1H), 7.13 (s, 1H), 7.10 (d, J=8.0Hz, 1H)13C NMR
(126MHz,CDCl3):δ165.34,165.25,163.15,153.32,137.55, 133.21,128.73,124.54,
122.21,119.65,116.21,113.43,110.65.HR-MS(ESI): m/z calcd for C15H9FO2([M+H]+)
240.0587,found 241.0659.
3- fluorophenyl benzo butyrolactone：Yield 81%, yellow solid；mp:136.1-137.2℃；1H NMR(500 MHz,
CDCl3) δ 8.26 (s, 1H), 8.16 (s, 1H), 7.55 (s, 1H), 7.52 (d, J=7.7Hz, 1H), 7.34 (m, 1H), 7.22
(d, J=7.9Hz, 1H), 7.32 (d, J=2.3Hz, 1H), 7.15 (s, 1H), 7.14 (d, J=8.0Hz, 1H)13C NMR
(126MHz,CDCl3):δ165.72,164.52,163.16,151.23, 139.69,135.52,125.76,124.36,
123.84,119.87,115.65,113.32,110.20.HR-MS (ESI):m/z calcd for C15H9FO2([M+H]+)
240.0587,found 241.0659.
4- fluorophenyl benzo butyrolactone：Yield 80%, yellow solid；mp:137.4-138.1℃；1H NMR(500MHz,
CDCl3) δ 8.30-8.17 (m, 2H), 7.59 (s, 1H), 7.54 (d, J=7.7Hz, 1H), 7.38-7.32 (m, 1H), 7.20
(d, J=7.9Hz, 1H), 7.18 (d, J=2.3Hz, 1H), 7.17 (s, 1H), 7.12 (d, J=8.0Hz, 1H)13C NMR
(126MHz,CDCl3):δ166.62,165.52,163.36,153.03, 138.89,134.51,129.75,125.33,
123.85,119.34,115.92,115.75,110.90.HR-MS (ESI):m/z calcd for C15H9FO2([M+H]+)
Its hydrogen of 240.0587, found 241.0659. spectrum, carbon spectrum and mass spectrogram are shown in Fig. 1,2 and 3 respectively.
2- aminomethyl phenyl benzo butyrolactone：Yield 81%, yellow oil；1H NMR(500MHz,CDCl3)δ7.98 (s,
1H), 7.65 (d, J=7.6Hz, 1H), 7.43 (t, J=6.8Hz, 1H), 7.39 (d, J=7.5 Hz, 1H), 7.32 (dd, J=
16.1,7.1Hz, 3H), 7.14 (d, J=8.1Hz, 1H), 6.99 (t, J=7.7Hz, 1H), 2.44 (s, 3H)13C NMR
(126MHz,CDCl3):δ168.68,154.45,140.06, 137.80,133.22,130.88,130.82,130.58,
128.26,125.85,123.77 122.93,121.99, 119.77,111.03,20.11.HR-MS(ESI):m/z calcd
for C16H12O2([M+H]+)236.0837, found 237.0910.
3- aminomethyl phenyl benzo butyrolactone：Yield 87%, yellow crystals；mp:155.2-156.2℃；1H NMR(500
MHz,CDCl3) δ 8.04 (d, J=7.8Hz, 1H), 7.98 (s, 1H), 7.61 (s, 1H), 7.54 (d, J=7.6Hz, 1H),
7.38 (t, J=7.7Hz, 1H), 7.36-7.31 (m, 1H), 7.30 (d, J=7.6 Hz, 1H), 7.18 (t, J=7.6Hz, 1H),
7.11 (d, J=8.0Hz, 1H), 2.44 (s, 3H)13C NMR(126MHz,CDCl3):δ165.90,153.00,140.63,
138.22,133.14,132.65,132.30, 129.77,129.19,128.52,125.54,123.70,120.57,
119.35,111.02,21.41.HR-MS (ESI):m/z calcd for C16H12O2([M+H]+)236.0837,found
237.0910.
4- aminomethyl phenyl benzo butyrolactone：Yield 75%, yellow solid；mp:156.8-157.7℃；1H NMR(500
MHz,CDCl3) δ 8.13 (d, J=8.2Hz, 1H), 7.86 (s, 1H), 7.80 (d, J=7.7Hz, 1H), 7.64-7.59 (m,
2H), 7.34 (d, J=7.7Hz, 2H), 7.15 (t, J=6.1Hz, 1H), 7.06 (td, J=7.7,0.9Hz, 1H), 2.46 (s,
3H).13C NMR(126MHz,CDCl3):δ169.18,154.42, 141.31,140.55,132.26,131.25,130.66,
129.57,123.65,122.73,122.09,119.21, 111.19,21.75.HR-MS(ESI):m/z calcd for
C16H12O2([M+H]+)236.0837,found 237.0910.
2- methoxyphenyl benzo butyrolactone：Yield 86%, yellow solid；mp:176.4-177.5℃；1H NMR(500
MHz,CDCl3) δ 8.04 (s, 1H), 7.72 (d, J=7.6Hz, 1H), 7.63 (d, J=7.7Hz, 1H), 7.49-7.43 (m,
1H), 7.32-7.27 (m, 1H), 7.09 (d, J=8.0Hz, 1H), 7.06-7.03 (m, 1H), 7.01 (d, J=7.9Hz, 1H),
6.98 (d, J=8.3Hz, 1H), 3.87 (s, 3H)13C NMR (126MHz,CDCl3):δ169.00,158.44,153.54,
137.41,132.63,130.56,129.52, 123.65,122.76,122.10,121.59,120.61,119.74,
111.19,110.78,55.67.HR-MS (ESI):m/z calcd for C16H12O3([M+Na]+)252.0786,found
275.0679.
3- methoxyphenyl benzo butyrolactone：Yield 81%, yellow solid；mp:172.1-172.2℃；1H NMR(500
MHz,CDCl3) δ 7.87 (s, 1H), 7.80 (d, J=7.8Hz, 1H), 7.62 (s, 1H), 7.45 (t, J=7.9Hz, 1H),
7.32-7.28 (m, 1H), 7.24-7.19 (m, 1H), 7.17 (d, J=8.0Hz, 1H), 7.09 (t, J=6.0Hz, 1H), 7.06
(dd, J=8.8,2.1Hz, 1H), 3.89 (s, 3H)13C NMR (126MHz,CDCl3):δ168.93,159.70,154.56,
140.83,135.29,130.99,129.94, 125.32,123.75,123.03,121.81,119.44,116.41,
114.41,111.24,55.44.HR-MS (ESI):m/z calcd for C16H12O3([M+Na]+)252.0786,found
275.0679.
4- methoxyphenyl benzo butyrolactone：Yield 83%, yellow solid；mp:174.5-175.4℃；1H NMR(500
MHz,CDCl3) δ 8.31 (d, J=8.8Hz, 2H), 7.57 (s, 1H), 7.53 (d, J=7.6Hz, 1H), 7.36 (dd, J=
13.3,5.3Hz, 1H), 7.20 (d, J=7.6Hz, 1H), 7.17 (d, J=8.0Hz, 1H), 7.01 (d, J=8.9Hz, 2H),
3.92(s,3H).13C NMR(126MHz,CDCl3):δ166.43, 162.02,152.60,140.32,134.71,131.78,
130.38,129.02,126.48,126.01,123.60, 122.34,118.90,114.24,110.63,55.51.HR-MS
(ESI):m/z calcd for C16H12O3([M+ Na]+)252.0786,found 275.0679.
2- hydroxy phenyl benzo butyrolactone：Yield 66%, yellow solid；mp:167.2-168.2℃；1H NMR(500
MHz,CDCl3) δ 7.82 (s, 1H), 7.79 (d, J=7.7Hz, 1H), 7.51 (d, J=5.5Hz, 2H), 7.42 (s, 1H),
7.42 (m, 1H), 7.21 (dd, J=3.3,2.1Hz, 1H), 7.16 (d, J=8.0 Hz, 1H), 7.08 (t, J=7.7Hz, 1H)
.13C NMR(126MHz,CDCl3):δ168.27,155.67, 152.93,137.48,135.44,132.29,130.55,
127.53,124.62,123.54,121.25,120.41, 120.11,119.68,114.03.HR-MS(ESI):m/z calcd
for C15H10O3([M+H]+)238.0630, found 239.0703.
3- hydroxy phenyl benzo butyrolactone：Yield 61%, yellow solid；mp:172.4-173.6℃；1H NMR(500
MHz,CDCl3) δ 7.81 (s, 1H), 7.75 (d, J=7.4Hz, 1H), 7.45 (d, J=5.5Hz, 2H), 7.41 (s, 1H),
7.27 (m, 1H), 7.21 (dd, J=3.3,2.1Hz, 1H), 7.15 (d, J=8.0 Hz, 1H), 7.10 (t, J=7.7Hz, 1H)
.13C NMR(126MHz,CDCl3):δ168.65,156.45, 152.96,138.98,135.42,132.29,131.65,
128.86,123.92,123.81,123.05,122.41, 121.55,118.58,110.09.HR-MS(ESI):m/z calcd
for C15H10O3([M+H]+)238.0630, found 239.0703.
4- hydroxy phenyl benzo butyrolactone：Yield 61%, yellow solid；mp:173.4-174.2℃；1H NMR(500
MHz,CDCl3) δ 7.86 (s, 1H), 7.82 (d, J=7.7Hz, 1H), 7.56 (d, J=5.5Hz, 2H), 7.48 (s, 1H),
7.42-7.37 (m, 1H), 7.24 (dd, J=3.3,2.1Hz, 1H), 7.18 (d, J=8.0Hz, 1H), 7.12 (t, J=
7.7Hz,1H).13C NMR(126MHz,CDCl3):δ169.25,154.65, 150.91,139.08,135.42,131.29,
130.05,126.83,123.92,123.51,123.25,122.41, 119.58,111.09.HR-MS(ESI):m/z calcd
for C15H10O3([M+H]+)238.0630,found 239.0703.
2- nitrobenzophenone benzo butyrolactone：Yield 66%, yellow solid；mp:187.6-188.2℃；1H NMR(500
MHz,CDCl3) δ 8.27 (d, J=8.9Hz, 1H), 8.03 (d, J=8.5Hz, 1H), 7.79 (s, 1H), 7.75 (d, J=
2.9Hz, 2H), 7.56 (d, J=7.8Hz, 1H), 7.42 (t, J=7.8Hz, 2H), 7.19 (d, J=8.1Hz, 1H), 7.09
(dd, J=11.2,4.2Hz, 1H)13C NMR(126MHz,CDCl3): δ156.07,142.50,138.15,136.44,
135.32,134.12,132.26,130.00,126.34, 124.54,124.38,123.23,122.94,122.57,
110.69.HR-MS(ESI):m/z calcd for C15H9NO5 ([M-H]+)283.0481,found 282.0408.
3- hydroxy phenyl benzo butyrolactone：Yield 63%, yellow solid；mp:189.4-189.2℃；1H NMR(500
MHz,CDCl3) δ 8.25 (d, J=8.9Hz, 1H), 8.23 (d, J=8.9Hz, 1H), 7.79 (s, 1H), 7.73 (d, J=
2.3Hz, 2H), 7.56 (d, J=7.8Hz, 1H), 7.42 (t, J=7.8Hz, 2H), 7.19 (d, J=7.1Hz, 1H), 7.01
(dd, J=10.2,4.2Hz, 1H)13C NMR(126MHz,CDCl3): δ156.57,143.59,138.34,136.84,
132.76,132.43,131.04,130.00,126.75, 124.71,124.48,123.64,122.64,122.54,
112.65.HR-MS(ESI):m/z calcd for C15H9NO5 ([M-H]+)283.0481,found 282.0408.
4- hydroxy phenyl benzo butyrolactone：Yield 64%, yellow solid；mp:186.4-187.2℃；1H NMR(500
MHz,CDCl3) δ 8.31 (d, J=8.9Hz, 1H), 8.26 (d, J=8.9Hz, 1H), 7.85 (s, 1H), 7.84 (d, J=
2.9Hz, 2H), 7.56 (d, J=7.8Hz, 1H), 7.42 (t, J=7.8Hz, 2H), 7.19 (d, J=8.1Hz, 1H), 7.08
(dd, J=11.2,4.2Hz, 1H)13C NMR(126MHz,CDCl3): δ155.07,140.50,139.12,136.84,
132.26,130.00,124.35,124.21,124.08, 123.64,122.94,120.17,111.74.HR-MS(ESI):m/
z calcd for C15H9NO5([M-H]+) 283.0481,found 282.0408.
2- cyano-phenyl benzo butyrolactone：Yield 62%, yellow solid；mp:134.5-135.2℃；1H NMR(500
MHz,CDCl3) δ 7.80 (d, J=8.2Hz, 3H), 7.78-7.71 (m, 2H), 7.56 (d, J=7.8Hz, 1H), 7.42 (m,
1H), 7.13 (d, J=8.1Hz, 1H), 7.07 (t, J=7.7Hz, 1H)13C NMR (126MHz,CDCl3):δ169.44,
155.65,138.21,135.21,132.66,132.70,129.80, 128.86,124.90,124.02,122.79,
121.07,118.28,115.65,110.69.HR-MS(ESI): m/z calcd for C16H9NO2([M-H]+)247.0633,
found 246.0561.
3- cyano-phenyl benzo butyrolactone：Yield 65%, yellow solid；mp:132.2-133.5℃；1H NMR(500
MHz,CDCl3) δ 7.81 (d, J=8.2Hz, 3H), 7.82-7.27 (m, 2H), 7.52 (d, J=7.8Hz, 1H), 7.42 (m,
1H), 7.14 (d, J=8.1Hz, 1H), 7.09 (t, J=7.7Hz, 1H)13C NMR (126MHz,CDCl3):δ169.11,
156.99,139.62,137.65,137.21,132.66,132.10, 129.80,124.40,124.02,123.89,
121.07,118.87,113.45,111.32.HR-MS(ESI): m/z calcd for C16H9NO2([M-H]+)247.0633,
found 246.0561.
4- cyano-phenyl benzo butyrolactone：Yield 62%, yellow solid；mp:137.6-138.6℃；1H NMR(500
MHz,CDCl3) δ 7.81 (d, J=8.2Hz, 3H), 7.79-7.75 (m, 2H), 7.56 (d, J=7.8Hz, 1H), 7.44-7.38
(m, 1H), 7.18 (d, J=8.1Hz, 1H), 7.07 (t, J=7.7Hz, 1H)13C NMR(126MHz,CDCl3):δ168.11,
154.99,138.62,137.38,132.66,132.10,129.80, 124.90,124.02,122.89,121.07,
118.18,113.65,111.68.HR-MS(ESI):m/z calcd for C16H9NO2([M-H]+)247.0633,found
246.0561.
4- ethylphenyl benzo butyrolactone：Yield 84%, yellow solid；mp:111.6-112.7℃；1H NMR(500
MHz,CDCl3) δ 8.16 (d, J=8.2Hz, 2H), 7.62 (s, 1H), 7.54 (dd, J=7.6,0.6 Hz, 1H), 7.33 (s,
2H), 7.31 (s, 1H), 7.18 (td, J=7.6,0.8Hz, 1H), 7.11 (d, J=8.0Hz, 1H), 2.75-2.70 (m, 2H),
1.28 (d, J=7.6Hz, 3H)13C NMR(126MHz, CDCl3):δ166.10,152.88,148.06,140.57,
132.38,130.77,129.53,128.22,125.70, 123.65,119.72,119.22,110.98,29.04,
15.22.HR-MS(ESI):m/z calcd for C17H14O2 ([M+Na]+)250.0994,found 273.0886.
4- trifluoromethyl benzo butyrolactone：Yellow oil；1H NMR(500MHz,CDCl3) δ 8.23 (d, J=
7.9Hz, 2H), 7.72 (d, J=7.8Hz, 2H), 7.65 (d, J=11.5Hz, 1H), 7.58 (d, J=7.1Hz, 1H), 7.41-
7.37 (m, 1H), 7.22 (t, J=7.1Hz, 1H), 7.14 (d, J=8.0 Hz, 1H)13C NMR(126MHz,CDCl3):δ
165.55,153.45,137.71,136.19,131.77, 130.83,127.31,127.27,125.43,124.73,
124.07,123.28,119.89,111.10.HR-MS (ESI):m/z calcd for C16H9F3O2([M+Na]+)
290.0555,found 313.0447.
Methyl benzo butyrolactone：Yield 86%, gray solid；mp:89.3-90.5℃；1H NMR(500MHz,CDCl3) δ
7.61-7.58 (m, 2H), 7.26 (td, J=7.8,1.3Hz, 1H), 7.14 (td, J=7.6,0.9 Hz, 1H), 7.09 (d, J=
7.8Hz,1H),4.15(s,3H).13C NMR(126MHz,CDCl3):δ169.68, 160.03,151.46,128.02,
124.46,122.64,122.48,110.20,103.47,63.67.HR-MS (ESI):m/z calcd for C10H8O2([M+
Na]+)160.0524,found 183.0416.
Ethyl benzo butyrolactone：Yield 82%, gray solid；mp:86.6-87.9℃；1H NMR(500MHz,CDCl3) δ
7.66 (s, 1H), 7.59 (t, J=6.3Hz, 1H), 7.24 (td, J=7.8,1.3Hz, 1H), 7.13 (td, J=7.6,
0.8Hz, 1H), 7.08 (d, J=8.0Hz, 1H), 4.36 (q, J=7.1Hz, 2H), 1.50 (t, J=7.1Hz, 3H)13C NMR
(126MHz,CDCl3):δ169.85,158.78,151.57, 127.89,123.65,122.69,122.65,110.12,
103.30,72.85,15.50.HR-MS(ESI):m/z calcd for C11H10O2([M+Na]+)174.0681,found
197.0573.
2- naphthyl benzo butyrolactone：Yield 84%, yellow solid；mp:188.2-189.7℃；1H NMR(500MHz,
CDCl3) δ 8.66 (s, 1H), 8.35 (dd, J=8.7,1.6Hz, 1H), 7.95 (d, J=7.9Hz, 1H), 7.93-7.88 (m,
1H), 7.86 (d, J=8.0Hz, 1H), 7.75 (d, J=9.0Hz, 1H), 7.58 (d, J=7.7Hz, 2H), 7.55 (dd, J=
4.3,1.4Hz, 1H), 7.39-7.32 (m, 1H), 7.23-7.17 (m, 1H), 7.13 (d, J=8.0Hz, 1H)13C NMR
(126MHz,CDCl3):δ166.03,153.06, 140.33,134.57,133.51,133.00,130.90,129.84,
129.30,128.15,128.12,128.07, 127.71,126.64,125.62,123.81,120.78,119.40,
110.85.HR-MS(ESI):m/z calcd for C19H12O2([M+H]+)272.0837,found 273.0910.
9- anthryl benzo butyrolactone：Yield 86%, yellow solid；mp:187.3-188.2℃；1H NMR(500MHz,
CDCl3) δ 8.69 (d, J=8.7Hz, 1H), 8.58 (s, 1H), 8.10 (d, J=8.4Hz, 2H), 8.02 (t, J=6.3Hz,
2H), 7.56-7.51 (m, 2H), 7.48 (dt, J=11.9,9.2Hz, 2H), 7.24-7.17 (m, 1H), 7.13 (d, J=
8.0Hz, 1H), 6.61 (t, J=7.6Hz, 1H), 6.00 (d, J=7.7 Hz, 1H)13C NMR(126MHz,CDCl3):δ
168.01,154.64,137.02,131.21,130.85, 129.37,129.20,128.91,127.25,127.07,
126.65,125.80,125.34,124.39,123.72, 121.97,110.74.HR-MS(ESI):m/z calcd for
C23H14O2([M+H]+)322.0994,found 323.1067.
4- isopropyl phenyl benzo butyrolactone：Yield 73%, yellow solid；mp:162.4-163.5℃；1H NMR(500
MHz,CDCl3) δ 7.86 (s, 1H), 7.84 (d, J=7.7Hz, 1H), 7.65 (d, J=8.1Hz, 2H), 7.36 (dd, J=
12.3,8.3Hz, 4H), 7.14 (d, J=8.0Hz, 1H), 3.01-2.96 (m, 1H), 1.33 (d, J=6.9Hz, 6H)13C
NMR(126MHz,CDCl3):δ169.24,154.41,152.19, 141.35,132.45,130.85,129.67,126.91,
123.67,122.78,122.09,119.26,111.18, 34.32,23.76.HR-MS(ESI):m/z calcd for
C18H16O2([M+Na]+)264.1150,found 287.1043.
2,4 dichloro-benzenes benzo butyrolactone：Yield 83%, yellow solid；mp:145.2-146.2℃；1H NMR(500
MHz,CDCl3) δ 7.84 (s, 1H), 7.71 (d, J=8.3Hz, 1H), 7.55 (d, J=1.9Hz, 1H), 7.42 (d, J=
7.7Hz, 1H), 7.38 (dd, J=8.5,2.3Hz, 2H), 7.14 (t, J=8.5Hz, 1H), 7.03 (t, J=7.7Hz, 1H)
.13C NMR(126MHz,CDCl3):δ167.96,154.80,136.83, 135.54,131.70,131.08,130.53,
130.26,127.99,127.17,124.42,123.87,122.92, 121.25,111.27.HR-MS(ESI):m/z calcd
for C15H8Cl2O2([M+H]+)289.9910,found 290.9974.
3,5 difluorobenzene benzo butyrolactone：Yield 82%, yellow solid；mp:156.3-157.2℃；1H NMR(500
MHz,CDCl3) δ 7.75 (d, J=6.8Hz, 2H), 7.55 (d, J=7.6Hz, 1H), 7.49 (s, 1H), 7.39 (t, J=
7.8Hz, 1H), 7.21 (t, J=7.6Hz, 1H), 7.13 (d, J=8.0Hz, 1H), 6.93 (t, J=8.5Hz, 1H)13C NMR
(126MHz,CDCl3):δ163.75,161.77,153.51, 136.73,135.71,130.92,124.60,124.06,
119.82,114.45,114.29,111.10,106.59, 106.39,106.19.HR-MS(ESI):m/z calcd for
C15H8F2O2([M+H]+)258.0492,found 259.0565.
The bromo- 4 fluorobenzene benzo butyrolactone of 2-：Yield 76%, yellow solid；mp:153.5-154.2℃；1H NMR(500
MHz,CDCl3) δ 7.78 (s, 1H), 7.74 (dd, J=8.6,5.9Hz, 1H), 7.46 (dd, J=8.1,2.5Hz, 1H), 7.38
(dd, J=7.9,2.9Hz, 2H), 7.20-7.15 (m, 1H), 7.14-7.11 (m, 1H), 7.01 (td, J=7.7,0.8Hz,
1H).13C NMR(126MHz,CDCl3):δ168.02,164.23, 162.20,153.98,137.85,131.53,131.14,
130.69,123.86,122.79,121.27,121.03, 120.84,115.11,111.23.HR-MS(ESI):m/z calcd
for C15H8BrFO2([M+H]+)317.9692, found 318.9765.
The chloro- 4 fluorobenzene benzo butyrolactone of 3-：Yield 74%, yellow solid；mp:152.2-153.5℃；1H NMR(500
MHz,CDCl3) δ 8.32 (dd, J=7.1,1.9Hz, 1H), 8.12 (ddd, J=8.3,4.5,2.0Hz, 1H), 7.53 (d, J=
7.6Hz, 1H), 7.51-7.46 (m, 1H), 7.35 (d, J=7.7Hz, 1H), 7.25-7.17 (m, 2H), 7.11 (d, J=
8.2Hz,1H).13C NMR(126MHz,CDCl3):δ165.78, 158.41,153.20,137.08,134.22,132.29,
130.44,124.90,123.98,122.65,121.78, 119.57,116.89,116.72,111.01.HR-MS(ESI):m/
z calcd for C15H8ClFO2([M+H]+) 274.0197,found 275.0270.
2- thiophene benzo butyrolactone：Yield 86%, yellow solid；mp:167.2-168.2℃；1H NMR(500MHz,
CDCl3) δ 7.89 (d, J=3.7Hz, 1H), 7.76 (s, 1H), 7.70 (d, J=5.1Hz, 1H), 7.50 (dd, J=7.6,
0.6Hz, 1H), 7.30 (td, J=7.9,1.2Hz, 1H), 7.17 (ddd, J=15.7,6.3,2.3Hz, 2H), 7.10 (d, J=
8.0Hz,1H).13C NMR(126MHz,CDCl3):δ166.47, 152.72,137.69,137.41,134.74,131.04,
129.34,127.93,125.12,123.75,119.05, 116.11,110.81.HR-MS(ESI):m/z calcd for
C13H8O2S([M+H]+)228.0245,found 229.0318.
2- furfural benzo butyrolactone：Yield 75%, yellow solid；mp:153.5-154.6℃；1H NMR(500MHz,
CDCl3) δ 8.26 (d, J=3.7Hz, 1H), 7.66 (d, J=1.5Hz, 1H), 7.52 (s, 1H), 7.50 (d, J=7.7Hz,
1H), 7.32 (td, J=7.9,1.1Hz, 1H), 7.17 (td, J=7.6,0.6Hz, 1H), 7.12 (d, J=8.0Hz, 1H),
6.71-6.64(m,1H).13C NMR(126MHz,CDCl3):δ 166.10,152.87,150.78,146.27,129.52,
125.04,124.52,123.76,120.77,119.18, 116.20,114.16,110.82.HR-MS(ESI):m/z calcd
for C13H8O3([M+H]+)212.0473, found 213.0546.
2- pyrroles's benzo butyrolactone：Yield 65%, gray solid；mp:177.2-178.5℃；1H NMR(500MHz,
CDCl3) δ 12.46 (s, 1H), 7.44 (s, 2H), 7.27-7.22 (m, 2H), 7.16 (t, J=7.5Hz, 1H), 7.11 (d, J=
7.9Hz, 1H), 6.84 (s, 1H), 6.43 (d, J=1.2Hz, 1H)13C NMR (126MHz,CDCl3):δ170.09,
151.98,129.78,128.48,127.58,126.96,125.97, 123.80,122.61,118.17,112.29,
110.57.HR-MS(ESI):m/z calcd for C13H9NO2([M +H]+)211.0633,found 212.0706.
3- indoles benzo butyrolactone：Yield 63%, yellow solid；mp:162.1-163.4℃；1H NMR(500MHz,
CDCl3) δ 9.40 (d, J=5.3Hz, 1H), 8.44 (dd, J=7.3,4.6Hz, 1H), 7.81-7.70 (m, 2H), 7.60-
(7.53 m, 1H), 7.43-7.35 (m, 2H), 7.30 (td, J=12.4,7.3Hz, 1H), 7.21-7.12 (m, 1H), 7.11-
7.03(m,1H).13C NMR(126MHz,CDCl3):δ169.54,167.30, 152.47,135.33,132.10,129.75,
129.42,127.51,126.06,125.18,124.49,123.82, 119.06,117.65,116.94,115.66,
110.72.HR-MS(ESI):m/z calcd for C17H11NO2([M +H]+)261.0790,found 262.0863.
2- pyridine benzo butyrolactone：Yield 64%, gray solid；mp:187.7-188.7℃；1H NMR(500MHz,
CDCl3) δ 9.12 (d, J=7.8Hz, 1H), 8.94-8.87 (m, 1H), 7.84 (td, J=7.7,1.8 Hz, 1H), 7.74 (s,
1H), 7.63 (d, J=7.8Hz, 1H), 7.45-7.40 (m, 1H), 7.37 (ddd, J=7.6,4.7,0.9Hz, 1H), 7.22
(td, J=7.7,0.9Hz, 1H), 7.15 (d, J=8.0Hz, 1H)13C NMR(126MHz,CDCl3):δ169.89,
155.19,153.15,149.89,137.87,136.87, 131.73,128.51,128.35,124.44,124.32,
123.99,122.45,110.55.HR-MS(ESI): m/z calcd for C14H9NO2([M+H]+)223.0633,found
224.0706. its hydrogen spectrum, carbon spectrum and mass spectrogram are shown in Fig. 4,5 and 6 respectively.
Cinnamic acid benzo butyrolactone：Yield 56%, yellow solid；mp:151.4-152.8℃；1H NMR(500MHz,
CDCl3) δ 8.35 (dd, J=15.5,11.7Hz, 1H), 7.60 (d, J=7.0Hz, 2H), 7.46 (d, J=7.6Hz, 1H),
7.42-7.33 (m, 4H), 7.29 (dd, J=12.1,4.4Hz, 1H), 7.14 (t, J=7.6Hz, 1H), 7.08 (t, J=
11.2Hz,2H).13C NMR(126MHz,CDCl3):δ166.91, 153.08,144.92,139.09,135.98,129.95,
129.66,128.97,128.13,124.52,123.86, 123.80,119.65,119.51,110.81.HR-MS(ESI):m/
z calcd for C17H12O2([M+Na]+) 248.0837,found 271.0370.
α-bromocinnamaldehyde：Yield 53%, yellow solid；mp:152.3-153.7℃；1H NMR(500MHz,CDCl3) δ
7.84 (d, J=8.2Hz, 2H), 7.50-7.45 (m, 3H), 7.32-7.27 (m, 3H), 7.16-7.13 (m, 1H), 7.12-
7.09(m,1H),7.09-7.07(m,1H).13C NMR(126MHz,CDCl3):δ154.89, 154.66,139.89,
135.32,134.86,132.12,129.73,128.88,128.77,128.68,126.60, 124.59,114.93,
111.56,111.03.HR-MS(ESI):m/z calcd for C17H11BrO2([M+Na]+) 325.9942,found
348.9834.
α-methylcinnamaldehyde：Yield 58%, yellow solid；mp:151.3-152.5℃；1H NMR(500MHz,CDCl3) δ
7.64 (d, J=8.1Hz, 3H), 7.54 (m, 2H), 7.35-7.26 (m, 3H), 7.19 (m, 1H), 7.17-7.03 (m, 1H),
7.1 (m, 1H), 2.53 (s, 3H)13C NMR(126MHz,CDCl3):δ167.67, 155.83,153.52,145.31,
142.99,140.85,130.06,129.77,129.45,129.09,128.64, 128.47,123.60,119.18,
110.79,22.93.HR-MS(ESI):m/z calcd for C18H14O2([M+ Na]+)262.0994,found
285.0886.
To trifluoromethylbenzene (3- fluorine) benzo butyrolactone：Yield 68%, yellow solid；mp:176.3-177.2℃；1H
NMR(500MHz,CDCl3) δ 8.10 (d, J=7.9Hz, 1H), 7.73 (d, J=7.8Hz, 2H), 7.45 (d, J=11.5Hz,
1H), 7.35 (d, J=7.1Hz, 2H), 7.32 (t, J=7.1Hz, 1H), 6.78 (d, J=8.0Hz, 1H)13C NMR
(126MHz,CDCl3):δ165.55,153.45,137.71,136.19, 131.77,130.83,127.31,127.27,
125.43,124.73,124.07,123.28,119.89,111.10. HR-MS(ESI):m/z calcd for C16H8F4O2
([M+H]+)308.0460,found 309.0530.
To trifluoromethylbenzene (3- triazoles) benzo butyrolactone：Yield 62%, yellow solid；mp:182.1-183.6℃；1H
NMR(500MHz,CDCl3) δ 7.73 (s, 1H), 7.45 (d, J=7.6Hz, 2H), 7.32 (d, J=7.1Hz, 2H), 7.28 (t,
J=7.1Hz, 1H), 6.93 (d, J=8.0Hz, 2H), 3.03-2.94 (m, 2H), 2.13 (s, 1H)13C NMR(126MHz,
CDCl3):δ162.20,150.92,139.83,138.65, 134.61,130.21,129.41,126.55,126.31,
125.43,125.01,124.61,120.78,119.31, 67.98,64.52.HR-MS(ESI):m/z calcd for
C18H12F3N3O2([M+H]+)359.0882,found 360.0952.
The biological activity determination example of 4 compounds
Experimental example 1：Growth rate method determines benzo butyrolactone derivative to botrytis cinerea and cucumber anthracnose
Suppression virulence
1. materials and methods
1.1 material to be tested
Tomato ash grape germ (Botrytis cinerea), cucumber anthracnose (Colletotrichum
Lagenarium) provided by Nuisanceless Pesticide Research Service Center, Xibei Agroforestry Science and T.Synthesized benzo butyrolactone
Analog derivative, 96% carbendazim active compound, Tween-20 (emulsifying agent)
1.2 test method
The preparation of potato dextrose agar (PDA culture medium)：By 400g after peeling potatoes, fritter is cut to
Add distilled water afterwards to boil 30 minutes, filtrate adds glucose 40g, 26~30g of agar powder after filtering, and distilled water is settled to
2000mL, pH=7,121 DEG C of autoclavings 30 minutes.
Different alpha-methylene-gamma-butyrolactone analog derivative medicaments is made into 10000 using mycelial growth rate method is suppressed
Mg/L concentration mother liquors, 1mL mother liquors are taken to be made with being cooled to pour into culture dish after 45 DEG C or so of PDA culture medium is well mixed
Concentration is 100mg/L drug containing flat board, is inoculated with different confession examination bacterium bacteria cakes (a diameter of 4mm) respectively after culture medium cooling, often
3 repetitions are handled, while set blank control and carbendazim medicament to compare, after cultivating 72~96h under conditions of being placed in suitably,
Using each colony growth diameter for examination bacterium of crossing method measurement, inhibiting rate is calculated with formula 1.With reagent agent quality
The logarithm value of concentration is independent variable (x), using the niqueMin of inhibiting rate as dependent variable (y), is obtained using least square method for reagent
The virulence regression equation of agent, and calculate the IC of each test compound50Value.
2. result and analysis
Benzo butyrolactone derivative is by suppressing mycelial growth rate method to botrytis cinerea and cucumber anthracnose
Inhibitory action the results are shown in Table 1.
Table 1:Suppression virulence of the benzo butyrolactone derivative to botrytis cinerea and cucumber anthracnose mycelial growth
From table 1 it follows that to trifluoromethylbenzene benzo butyrolactone and 4- fluorobenzene benzo butyrolactone EC50Value is respectively
2.02 μ g/mL and 2.41 μ g/mL are suitable with comparison medicament carbendazim.Derivatives active containing electron withdraw group, which slightly above contains, to be given
The compound of electron group, if 2- chlorobenzenes benzo butyrolactone compound is to the bacteriostatic activity (EC of botrytis cinerea50It is worth for 5.65
μ g/mL) it is higher than compound 2- methoxybenzene benzo butyrolactone (EC50It is worth for 15.64 μ g/mL).Set after structure activity study
Two compounds of meter are to trifluoromethylbenzene (3- fluorine) benzo butyrolactone (EC50It is worth for 1.32 μ g/mL) and to trifluoromethylbenzene
(3- triazoles) benzo butyrolactone (EC50It is worth for 1.14 μ g/mL) it is more apparently higher than comparison medicament to the bacteriostatic activity of tomato gray mould
Bacterium spirit (EC50It is worth for 1.6 μ g/mL).
Experimental example 2:Biological tissue method determines protection virulence of the part benzo butyrolactone compound to graw mold of tomato
1. materials and methods
1.1 material to be tested
Tomato ash grape germ (Botrytis cinerea) is by Xibei Univ. of Agricultural ＆ Forest Science ＆ Technology's public nuisance-free agricultural chemicals research service
Center provides；Tomato gray mould fruit, pick up from Yang Ling Yangchuan village township plastic greenhouse.Part benzo butyrolactone derivative, bacterium more than 96%
Clever active compound, Tween-20 (emulsifying agent).
1.2 test method
Using the progress of tomato young fruit method, (method refers to Fang Zhongda to the protection test of pesticide effectiveness to graw mold of tomato, plants disease research
Method [M] Beijing:Agriculture publishing house third edition .1995).Concrete operations are：Any bactericide is not applied by what is gathered from field
The tamato fruit of agent, first with clear water washes clean, dry, then 75% ethanol fruit surface is taken with the absorbent cotton libation at an ancient wedding ceremony, carried out
Sterilization treatment.The medicament diluted is sprayed directly on by fruit surface using spray-on process on tomato surface, after decoction dries i.e.
Start to connect bacterium.When connecing bacterium, that diameter about 0.5cm is pierced out on tamato fruit surface with transfer needle infects region, with sharp ash arrhizus bacteria
Infect, diameter 0.4cm bacteria cake is tipped upside down on into tamato fruit surface.23 DEG C of moisturizing culture 6d of tomato young fruit after bacterium are met, are surveyed
Colony diameter is measured, bacteriostasis rate is calculated using below equation.
Colony growth diameter (cm)=actual measurement colony diameter -0.4
2. result and analysis
20 kinds of benzo butyrolactone derivatives are determined to graw mold of tomato using biological tissue method (tomato young fruit method)
Protective effect, it the results are shown in Table shown in 2.
Protection virulence of the benzo butyrolactone derivative of table 2 to graw mold of tomato
As can be seen from the table, introducing heterocycle and unsaturated bond can significantly improve the protective effect effect to tomato gray mould；
Equally, introducing is disubstituted can also significantly improve activity.Such as：The EC of 2- thiophene benzo butyrolactone in this experiment50It is worth and is
6.98 μ g/mL, the EC of the cinnamic acid benzo butyrolactone of compound containing unsaturated double-bond50It is worth for 3.78 μ g/mL, hence it is evident that taken higher than nothing
The EC of Dai Ji compound phenyl benzo butyrolactone50It is worth for 12.65 μ g/mL.The disubstituted bromo- 4 fluorobenzene benzo fourths of compound 2-
The EC of lactone50It is worth and is also significantly improved for protective effects of the 3.84 μ g/mL to botrytis cinerea；Chemical combination after structure of modification
Thing is to trifluoromethylbenzene (3- fluorine) benzo butyrolactone and to trifluoromethylbenzene (3- triazoles) benzo butyrolactone (EC50Value is respectively
1.46 μ g/mL and 1.23 μ g/mL) protective effect to botrytis cinerea is apparently higher than comparison medicament carbendazim.
Experimental example 3：The potted plant experiment of 8 kinds of benzo butyrolactone compound preventing and treating wheat powdery mildews
1. materials and methods
1.1 material to be tested
Wheat powdery mildew (Erysiphe graminis), by Xibei Univ. of Agricultural ＆ Forest Science ＆ Technology's public nuisance-free agricultural chemicals research service
Center provides；Test plant host material is the susceptible variety of wheat Shan -451, is carried by Xibei Univ. of Agricultural ＆ Forest Science ＆ Technology's wheat center
For.Part benzo butyrolactone derivative, 50% Sukeling WP, Tween-20 (emulsifying agent).
1.2 test method
The wheat seed of 10~15 vernalization is sowed in every nutritive cube, when hot-house culture is to when wheat length to the two leaf phase
Carry out treatment and protective effect experiment.Dispenser is carried out with conventional spray, each processing sets 3 repetitions, if solvent control and clear water
Control.
Wheat powdery mildew inoculation is carried out using spore dithering, it is 18 ± 1 DEG C that the wheat after processing, which is placed in temperature, illumination/
Cultivated under the conditions of dark=8h/16h, according to disease a situation arises classification investigation, calculate it is each processing disease index and preventing and treating imitate
Fruit.
Therapeutic action, bacterium is first connect, carry out spray processing, culture after 24h again；Protective effect, first spray handle, after 24h again
Bacterium is connect, blade incidence is checked after cultivating 8d and records, as follows statistics, result of calculation.
(Fang Zhong plants sick research method [M] Beijing to the grade scale (in units of blade) of wheat powdery mildew up to:Agricultural goes out
Version society third edition .1995)：
0 grade：Blade face disease-free spot；
1 grade：Only a small amount of limited mycelium, no spore on blade；
2 grades：The blade face mycelia scale of construction is medium, there is some spores, organizes slight necrosis and chlorisis；
3 grades：Mycelial amount is medium or a lot, and amount is limited caused by spore, there is some necrosis and chlorisis；
4 grades：Sorus is very big, produces a large amount of spores, without necrosis.
2. result and analysis
Preventive and therapeutic effect effect of 8 kinds of benzo butyrolactone derivatives to wheat powdery mildew is tested using pot-culture method, as a result
It is shown in Table 3.
Potted plant test of pesticide effectiveness result (8d) of the 38 kinds of benzo butyrolactone derivatives of table to wheat powdery mildew
Note：1. data are the average value of 3 repetitions in table；2. the drug effect of benzo butyrolactone derivative calculates and uses solvent
Control, the drug effect of Sukeling calculates to be compareed using clear water；3. in preventive effect column, represented with different lowercase persons are marked after column of figure
In 0.05 horizontal upper significant difference in variance analysis (Duncan's methods).
5th, the preparation of the various preparations of the derivative of butyrolactone containing benzo
The various preparations of the derivative of butyrolactone containing benzo are carried out by pesticide standard processing method, contained in various formulations
The percentage by weight of composition is as follows：
| Formulation | Benzo butyrolactone derivative % | Filler or solvent % | Surfactant % |
| Wettable powder | 10~90 | 0~70 | 1~10 |
| Missible oil | 5~50 | 30~95 | 5~35 |
| Microemulsion | 10~50 | 30~80 | 1~30 |
| Soluble liquid | 1~70 | 0~80 | 1~35 |
| Aqua | 1~80 | 0~80 | 1~35 |
| Water dispersible granules | 1~90 | 0~80 | 1~35 |
| Aqueous emulsion | 1~80 | 0~80 | 1~35 |
| Suspending agent | 1~80 | 0~80 | 1~35 |
Filler therein can be the abilities such as clay, clay, kaolin, talcum powder, white carbon, bentonite and silicon bath soil
One or more kinds of mixtures in material known to field technique personnel；
Solvent can be water, methanol, just ethanol, (different) propyl alcohol, ethyl acetate, the ability such as benzene, toluene and other aromatic hydrocarbon
One or more kinds of mixtures in material known to field technique personnel；
Surfactant can be well known to a person skilled in the art and conventional all kinds of surface reactive materials one kind or
More than one mixture.As calcium dodecyl benzene sulfonate, styrene acid APEO, ethoxylated dodecyl alcohol are pungent
The table such as base phenol polyoxyethyl ether, pull open powder, saponin, lignin, Sulfonates material, alkyl sulfonates material and laruyl alcohol
One or more kinds of mixtures of face activating agent.
Other auxiliary agents include wetting agent, emulsifying agent, dispersant, sticker, stabilizer and synergist.
Wherein wetting agent can be that well known to a person skilled in the art thing for tea seed cake, spent pulping liquor, washing powder and pull open powder etc.
One or more kinds of mixtures in matter；
Emulsifying agent can be alkyl benzene sulfonate, APES class, phenethyl phenol polyethenoxy ether class, this
Well known to a person skilled in the art one or more kinds of mixtures in material for Pan's series, tween etc.；
Dispersant can be blackstrap, spent pulping liquor concentrate etc. well known to a person skilled in the art one kind in material or
More than one mixture；
Adhesive agent can be that well known to a person skilled in the art one or more kinds of in material for gelatinized corn starch, gelatin etc.
Mixture；
Stabilizer can be that well known to a person skilled in the art one in material for epoxychloropropane, ethylene glycol, glycerine etc.
Kind or more than one mixture；
Synergist can be the those skilled in the art such as organosilicon, Butacide, Octacide 264, alkyl carbonate, azone
One or more kinds of mixtures in known material.
It is the specific embodiment that inventor provides below.
Prepare embodiment 1：The preparation of 20% rubigan benzo butyrolactone missible oil
At room temperature, 2g rubigan benzo butyrolactone is weighed, adds 2mL acetone solutions, 2mL Tween-20s is added, adds water
10mL is settled to, is sufficiently stirred, shakes up.Produce 20% rubigan benzo butyrolactone missible oil.
Prepare embodiment 2：The preparation of 5% cinnamic acid benzo butyrolactone wettable powder
1g cinnamic acid benzo butyrolactone is weighed, physical crushing, crosses 200 mesh sieves.Add 0.2g DBSAs
Sodium, 0.5g sodium cellulose glycolates and 18.3g cross 200 mesh sieve talcum powder, fully mix.It is made in 5% cinnamic acid benzo fourth
Ester wettable powder.
Prepare embodiment 3：The preparation of 5%3,5 difluorobenzene benzo butyrolactone microemulsions
1g3 is weighed, 5 difluorobenzene benzo butyrolactone, adding the stirring of 2mL acetone makes it fully dissolve, and then adds 5mL OP-
10,1mL Tween-20s, surplus water polishing, 800-1000 revs/min of stirring 20-30 minute, you can 5%3,5 difluorobenzenes are made
Benzo butyrolactone microemulsion.
Prepare embodiment 4：The preparation of 5% pair of fluorobenzene benzo butyrolactone soluble liquid
1g is weighed to fluorobenzene benzo butyrolactone, at 20-25 DEG C, after adding 2mL acetone solutions, adds 2mL Tween-20s,
10mL methanol and 5mL cyclohexanone, fully shake up.It can be prepared by 5% pair of fluorobenzene benzo butyrolactone soluble liquid.
Prepare embodiment 5：The preparation of 10%2- pyrroles's phenyl benzo butyrolactone aqua
1g 2- pyrroles's phenyl benzo butyrolactone is weighed, after adding 1mL acetone solutions, adds 1mL Tween-20s, 1mL OP-
10 and 6mL water, fully shakes up.It can be prepared by 10%2- pyrroles's phenyl benzo butyrolactone aqua.
Prepare embodiment 6：The preparation of 5% p-trifluoromethyl phenyl benzo butyrolactone water dispersible granules
1g p-trifluoromethyl phenyl benzo butyrolactone is weighed, after adding 1mL acetone solutions, adds 1mL Tween-20s, and
7mL water, fully shakes up.0.2g neopelexes, 6g white carbons and 12.6g gelatin are added, squeezes block, is dried.It can make
Obtain 5% p-trifluoromethyl phenyl benzo butyrolactone water dispersible granules.
Prepare embodiment 7：The preparation of 5%2- thiophenyl's benzo butyrolactone aqueous emulsions
1g 2- thiophenyl's benzo butyrolactone is weighed, after adding 3mL acetone solutions, adds 1mL Tween-20s, 5mL OP-
10 and 1mL glycerine, surplus water polishing after stirring, 800-1000 revs/min of stirring 20-30 minute, you can 5%2- is made
Thiophenyl's benzo butyrolactone aqueous emulsion.
Prepare embodiment 8：The preparation of 5% fluorophenyl benzo butyrolactone suspending agent
Fluorophenyl benzo butyrolactone between 1g is weighed, after adding 2mL acetone solutions, adds 2mL Tween-20s, 0.5g methylols
Sodium cellulosate, 1.5mL glycerine, 13mL water, 800-1000 revs/min of stirring 20-30 minute, you can 5% fluorophenyl is made
Benzo butyrolactone suspending agent.
Prepare embodiment 9：20% p-trifluoromethyl phenyl benzo butyrolactone carbendazim (1:1) preparation of missible oil
At room temperature, 0.5g p-trifluoromethyl phenyl benzo butyrolactone and the carbendazim active compounds of 0.52g 96% are weighed respectively, are added
After entering 2mL acetone solutions, 2mL Tween-20s are added, 1g neopelexes is added, adds water to be settled to 10mL, fully shake
It is even.It can be prepared by 20% p-trifluoromethyl phenyl benzo butyrolactone Bravo (1:1) missible oil.
The 1.4 kinds of benzo butyrolactone derivative EC graw mold of tomato field efficacy experiments of application experiment example
1. materials and methods
1.1 material to be tested
10% m-chloro benzo butyrolactone missible oil, 10%2- thiophene benzo butyrolactone missible oil, the chloro- 4 fluorobenzene benzo fourths of 10%3-
Interior emulsifiable concentrate, 10% pair of trifluoromethylbenzene (3- fluorine) benzo butyrolactone missible oil, 80% carbendazol wettable powder；Tomato greenhouse
Greenhouse gardening；Tomato ash grape germ (Botrytis cinerea) is by Xibei Univ. of Agricultural ＆ Forest Science ＆ Technology's public nuisance-free agricultural chemicals research clothes
Business center provides.
1.2 test method
Double dilution method carries out decoction configuration；Per cell water 1.85L.
Therapeutic action, first it is inoculated with, carries out spray processing after 24h again；Protective effect, first spray handle, inoculate after 24h.
8d checks blade incidence and recorded.Recorded according to tomato gray mould severity Scaling standard survey, calculate the state of an illness
Index and prevention effect.
Severity Scaling presses following standard：
Leaf portion is killed stage division (in units of blade)
0 grade：Disease-free spot；
1 grade：Single blade scab has 3；
3 grades：Single blade scab has 4-6；
5 grades：Single blade scab has 7-10；
7 grades：Single blade scab has 11-20, and part is intensive in flakes.
9 grades：Single blade has scab is intensive to account for blade face more than 1/4.
Disease index calculation formula and prevention effect calculation formula are as follows：
In formula：CK0、CK1For the forward and backward disease index of blank district dispenser, PT0、PT1For the forward and backward disease for the treatment of region dispenser
Feelings index.
2. result and analysis
4 kinds of benzo butyrolactone derivatives are tested to graw mold of tomato crop field effect experiment effect, knot using pot-culture method
Fruit is shown in Table 4.
4. 4 kinds of benzo butyrolactone derivatives of table are to graw mold of tomato crop field effect experiment result (7d)
Note：1. data are the average value of 3 repetitions in table；2. in preventive effect column, with marking different lowercase persons after column of figure
Represent in variance analysis (Duncan's methods) in 0.05 horizontal upper significant difference.
Four kinds of benzo butyrolactone derivatives are respectively provided with higher field to tomato gray mould blade and prevented as can be seen from the above table
Effect.The chloro- 4 fluorobenzene benzo butyrolactone EC of 10%3-, 10% couple of trifluoromethylbenzene (3- fluorine) benzo butyrolactone EC dilute 500 times of fields
Between preventive effect and commodity medicament 80% carbendazol wettable powder, 1000 times of liquid it is suitable to the preventive effect of graw mold of tomato.
Application experiment example 2：8 kinds of benzo butyrolactone derivative formulations preventing and treating wheat scab field efficacy experiments
1. materials and methods
1.1 material to be tested
20% pair of fluorobenzene and butyrolactone missible oil (numbering ZX-1), 5% p-nitrophenyl and butyrolactone wettable powder (numbering
ZX-2), 5%2- naphthyls benzo butyrolactone microemulsion (numbering ZX-3), 5% cinnamic acid benzo butyrolactone soluble liquid (numbering
ZX-4), 10% pair of trifluoromethylbenzene benzo butyrolactone (numbering ZX-5), 5%3,5 difluorobenzene benzo butyrolactone (numbering ZX-6),
In 5% pair of trifluoromethylbenzene (3- fluorine) benzo butyrolactone (numbering ZX-7), 20% pair of trifluoromethylbenzene (3- triazoles) benzo fourth
Ester Bravo (1:1) missible oil (numbering ZX-8), 80% carbendazol wettable powder；Miscellaneous No. 4 of cucumber Tianjin, warmhouse booth kind
Plant；Fusarium graminearum.
1.2 test method
A, cell is set
If 18 processing, 3 repetitions, totally 54 cells, random district's groups arrangement, each plot area：6.2m × 1.0m=
6.2m2。
B, investigation method
4 points of investigation are taken per cell right-angled intersection, investigate two plants, and every plant is investigated whole blades, and calculation formula is as follows at every：
The grade scale of wheat scab (in units of blade)：
0 grade：Blade face disease-free spot；
1 grade：Only a small amount of limited mycelium, no spore on blade；
2 grades：The blade face mycelia scale of construction is medium, there is some spores, organizes slight necrosis and chlorisis；
3 grades：Mycelial amount is medium or a lot, and amount is limited caused by spore, there is some necrosis and chlorisis；
4 grades：Sorus is very big, produces a large amount of spores, without necrosis.
2. result and analysis
8 kinds of benzo butyrolactone derivative formulations preventing and treating wheat scab field efficacy experimental results are shown in Table 5.
5. 8 kinds of benzo butyrolactone derivative formulations preventing and treating wheat scab field efficacy experiments of table
Note：1. data are the average value of 3 repetitions in table；2. in preventive effect column, with marking different lowercase persons after column of figure
Represent in variance analysis (Duncan's methods) in 0.05 horizontal upper significant difference.
As can be seen from the above table, 8 kinds of benzo butyrolactone derivative formulations are respectively provided with higher field to wheat scab
Preventive effect.Wherein mixture preparation -- 20% pair of trifluoromethylbenzene (3- triazoles) benzo butyrolactone Bravo (1:1) missible oil (numbering
ZX-8 1000 times) are diluted, simultaneously butyrolactone missible oil (numbering ZX-1) dilutes 500 times of field efficacies and commodity medicament to 20% pair of fluorobenzene
80% carbendazol wettable powder dilution, 1000 times of preventive effects to wheat scab are suitable, and difference is not notable, and 20% pair of trifluoro
Methylbenzene (3- triazoles) benzo butyrolactone Bravo (1:1) 500 times of field efficacies of missible oil (numbering ZX-8) dilution are higher than commodity
The carbendazol wettable powder of medicament 80% dilutes 1000 times of preventive effects to wheat scab, significant difference.
Claims (10)
1. benzo butyrolactone derivative, it is characterised in that shown in the general structure of the analog derivative such as formula (one)：
R is selected from monosubstituted phenyl, disubstituted aryl, the direct-connected alkyl of saturation, heterocyclic aryl containing S, heterocyclic aryl containing N, the virtue of heterocycle containing O
One kind in base and polyaromatic.
2. benzo butyrolactone derivative as claimed in claim 1, it is characterised in that R is selected from any knot as shown in table 1
Structure：
Table 1
3. the synthetic method of the benzo butyrolactone derivative described in claim 1 or 2, it is characterised in that including by adjacent hydroxyl
The mol ratio of phenylacetic acid and p-methyl benzenesulfonic acid is 10:Backflow 4h obtains benzofuranone at 120~130 DEG C after 1 mixing；Benzo
The mol ratio of furanone and substituted benzaldehyde is 1:10ml triethylamines are added after 2 mixing and 15ml acetic anhydrides flow back at 80 DEG C
12h obtains reaction product, and reaction product produces benzo butyrolactone derivative after abstraction purification.
4. benzo butyrolactone derivative, it is characterised in that the compound including formula (two) and formula (three),
5. the synthetic method of the benzo butyrolactone derivative described in claim 4, it is characterised in that described formula (two) and formula
(3) preparation method of compound includes：
After being mixed to R septichens 50mmol, sulphur powder 100mmol and p-methyl benzenesulfonic acid 1.75mmol at 120~130 DEG C
Flow back 8h, add mass concentration be 20% sodium hydrate aqueous solution 10ml and four butyl bromation amine 1.25mmol at 100 DEG C
Lower hydrolysis 8h, regulation pH obtain 3-R o-hydroxy phenylacetic acids for 7；
5mmol 3-R o-hydroxy phenylacetic acids stir 16h with 15mL phosphorus oxychlorides in 50mL dichloromethane, and obtained product is through water
Wash drying and obtain 3-R benzofuranones after purification；
1.5mmol 3-R benzofuranones and 3mmol's adds 10mL concentration in the environment that pH is 8 to trifluro benzaldehyde and is
Simultaneously the crude product that 14h is obtained is stirred at room temperature in 10mol/L potassium hydroxide-ethanol solutions, and the pH for adjusting crude product is 7, then will be thick
Product is successively through extracting, washing, drying and obtaining after purification to trifluoromethylbenzene (3-R) benzo butyrolactone；
R is fluorine or triazole.
6. the benzo butyrolactone derivative described in claim 1,2 or 4 is used for the application for preparing bactericide.
7. application as claimed in claim 6, it is characterised in that described benzo butyrolactone derivative, which can be used for preparing, to be prevented and treated
The pesticidal preparations of the plant disease as caused by plant pathogenic fungi.
8. application as claimed in claim 7, it is characterised in that the microbial plant disease of described phytonosis includes：It is small
Wheat powdery mildew, wheat scab, take-all, wheat sharp eyespot, the leaf blight of corn, rice sheath blight disease, rice blast, cotton
Flower damping-off, Phytophthora capsici disease, graw mold of tomato, leaf muld of tomato, tomato morning late blight, cucumber anthracnose, cucumber fusarium axysporum
And sclerotinia sclerotiorum.
9. application as claimed in claim 7, it is characterised in that the form of described pesticidal preparations includes wettable powder, breast
Oil, microemulsion, soluble liquid, aqua, water dispersible granules, aqueous emulsion, granule and suspending agent.
10. application as claimed in claim 7, it is characterised in that described pesticidal preparations kill with Bravo or other commercializations
Microbial inoculum mixture be made compound wettable powder, missible oil, microemulsion, soluble liquid, aqua, water dispersible granules, aqueous emulsion,
Granula or suspending agent.
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| CN113698378A (en) * | 2021-10-05 | 2021-11-26 | 青岛农业大学 | Naphthoquinone compounds and preparation and acaricidal and bactericidal application thereof |
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| EP0921435A1 (en) * | 1997-12-02 | 1999-06-09 | Imation Corp. | Light-sensitive silver halide photographic elements containing yellow filter dyes |
| CN1427990A (en) * | 2000-04-04 | 2003-07-02 | 拜尔公司 | Use of light-absorbing compounds in information layer of optical data carriers, and optical data carriers |
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Cited By (3)
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| CN111057031A (en) * | 2019-12-23 | 2020-04-24 | 江苏长青农化股份有限公司 | Preparation method of benzofuranone |
| CN113698378A (en) * | 2021-10-05 | 2021-11-26 | 青岛农业大学 | Naphthoquinone compounds and preparation and acaricidal and bactericidal application thereof |
| CN113698378B (en) * | 2021-10-05 | 2023-01-17 | 青岛农业大学 | Naphthoquinone compounds, preparation thereof and mite-killing and sterilizing application thereof |
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