CN113666852A - Preparation method and application of beta-sulfonyl fluoroketone and derivative thereof - Google Patents
Preparation method and application of beta-sulfonyl fluoroketone and derivative thereof Download PDFInfo
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Abstract
The invention discloses beta-sulfonyl fluoroketone and derivatives thereof, and preparation methods thereof, tests prove that the beta-sulfonyl fluoroketone and the derivatives thereof have good effect of killing nematodes, the beta-sulfonyl fluoroketone and the derivatives thereof have good effect of inhibiting anthrax bacteria, the beta-sulfonyl fluoroketone and the derivatives thereof have simple structure, low cost and wide application prospect, and the synthesis method creatively uses alkyne and sulfonyl fluorine chloride as raw materials under electrochemical conditions to obtain a target compound through free radical reaction, thereby greatly shortening the synthesis steps, improving the reaction efficiency, having simple operation, mild conditions and high yield.
Description
Technical Field
The invention relates to the technical field of chemical synthesis and pesticides, in particular to a preparation method and application of beta-sulfonyl fluoroketone and derivatives thereof.
Background
Pine nematode disease, also known as "cancer of pine". This condition is caused by pine wood nematodes, which can cause significant economic losses. Pine nematode disease has developed into a global pine crisis since its first discovery in the last century. Meanwhile, for the prevention and treatment of nematodes, the anthrax is called as the eighth important plant pathogenic fungus, has great threat to tropical fruit trees, fir and the like, and causes high loss every year. Therefore, the research and development of novel medicaments for preventing and treating nematodes and anthrax have important values, only one example of the synthesis method of the beta-sulfonyl fluoroketone is reported at present, about 4 steps are needed, and the yield is low, so that the research on searching for a proper synthesis method of the beta-sulfonyl fluoroketone becomes a research subject which needs to be solved urgently at present, and therefore, the preparation method and the application of the beta-sulfonyl fluoroketone and derivatives thereof are brought about.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method and application of beta-sulfonyl fluoroketone and derivatives thereof
In order to achieve the purpose, the invention provides the following technical scheme:
the structure of the beta-sulfonyl fluoroketone is shown as the formula I and the formula II:
the R1 group in formula I includes, but is not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
the R2 group in formula I includes, but is not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
the R3 group in formula II includes but is not limited to phenyl, substituted phenyl, heterocyclic substituent, alkyl.
The structure of a beta-sulfonyl fluoroketone derivative is shown as a formula III:
the R1 group in formula III includes, but is not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
r2 groups include, but are not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
the R3 group includes, but is not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl.
A preparation method of beta-sulfonyl fluoroketone compounds shown in a formula I comprises the following steps:
step 1: adding alkyne, sulfonyl fluorine chloride, lithium perchlorate and ether into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is finished, the reaction solution is concentrated and then separated by column chromatography to obtain a target product;
a preparation method of beta-sulfonyl fluoroketone and a compound shown in a formula II comprises the following steps:
step 1: adding alkyne, sulfonyl fluorine chloride, lithium perchlorate and tetrahydrofuran into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is finished, the reaction solution is concentrated and then separated by column chromatography to obtain the target product.
A preparation method of a beta-sulfonyl fluoroketone derivative comprises the following steps:
step 1: adding beta-sulfonyl fluoroketone, hydrazine, acetonitrile and water into a reaction bottle, and stirring at room temperature;
step 2: after the reaction is finished, concentrating the reaction solution, and then carrying out column chromatography separation to obtain the target product.
Preferably, the molar ratio of alkyne to sulfonyl fluoride chloride is in the range of 1: 0.1 to 1: 10, the molar ratio of alkyne to lithium perchlorate is in the range of 1: 0.1 to 1: 100, the ether can be replaced by other solvents, including but not limited to tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane, ethylene glycol monomethyl ether, the solubility of the formed reaction solution is selected from 0.001M to 2M, the graphite flake of the electrode sheet material can be replaced by other materials, including but not limited to zinc metal, iron metal, nickel metal, copper metal, magnesium metal, aluminum metal, platinum metal, graphite felt, the voltage range is 1V to 36V, and the reaction time is 1 hour to 24 hours.
Preferably, the molar ratio of beta-sulfonyl fluoroketone to hydrazine is in the range of 1: 0.1 to 1: 10, the ratio of acetonitrile to water is 1: 0.1 to 1: 10, the stirring temperature is 20 ℃ to 100 ℃, and the reaction time is 1 hour to 48 hours.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the synthesis method of the beta-sulfonyl fluoroketone compound, provided by the invention, the target compound is obtained through radical reaction by using alkyne and sulfonyl fluorine chloride as raw materials under an electrochemical condition creatively, so that the synthesis steps are greatly shortened, the reaction efficiency is improved, the operation is simple, the condition is mild, and the yield is high;
2. experiments prove that the beta-sulfonyl fluoroketone and the derivative thereof have good nematode killing effect, the beta-sulfonyl fluoroketone and the derivative thereof have good anthrax bacteria inhibiting effect, and the beta-sulfonyl fluoroketone and the derivative thereof have simple structures, low cost and wide application prospects.
Drawings
FIG. 1 is a table of kill rates for test example 1 of the present invention;
FIG. 2 is a photograph of nematode solution treated with 1b according to test example 1 of the present invention;
FIG. 3 is a photograph of a nematode solution treated with 1c in test example 1 of the present invention;
FIG. 4 shows the inhibitory effect of compounds 1a to 1c of test example 2 of the present invention on anthrax bacteria;
FIG. 5 shows the inhibitory effect of compounds 1d-1e of test example 2 of the present invention on anthrax bacteria.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a technical scheme that: the structure of the beta-sulfonyl fluoroketone is shown as the formula I and the formula II:
the R1 group in the formula I includes but is not limited to phenyl, substituted phenyl (including mono-substituted phenyl and multi-substituted phenyl, the substituent includes but is not limited to halogen, carbonyl, ester group, aldehyde group, nitro, trifluoromethyl, trifluoromethoxy, methylmercapto, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl and the like), heterocyclic substituent (including but not limited to furan ring, thiophene ring, pyridine ring and the like), alkyl and the like; the R2 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, etc.; the R3 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, and the like;
the R2 group in the formula I includes but is not limited to phenyl, substituted phenyl (including mono-substituted phenyl and multi-substituted phenyl, the substituent includes but is not limited to halogen, carbonyl, ester group, aldehyde group, nitro, trifluoromethyl, trifluoromethoxy, methylmercapto, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl and the like), heterocyclic substituent (including but not limited to furan ring, thiophene ring, pyridine ring and the like), alkyl and the like; the R2 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, etc.; the R3 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, and the like;
the R3 group in formula II includes but is not limited to phenyl, substituted phenyl (including mono-substituted phenyl and multi-substituted phenyl, the substituent includes but is not limited to halogen, carbonyl, ester group, aldehyde group, nitro, trifluoromethyl, trifluoromethoxy, methylmercapto, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl, etc.), heterocyclic substituent (including but not limited to furan ring, thiophene ring, pyridine ring, etc.), alkyl, etc.; the R2 group includes but is not limited to phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, the substituents include but are not limited to halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylmercapto, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including but not limited to furan ring, thiophene ring, pyridine ring, etc.), alkyl, etc.; the R3 groups include, but are not limited to, phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan rings, thiophene rings, pyridine rings, etc.), alkyl, and the like.
The structure of a beta-sulfonyl fluoroketone derivative is shown as a formula III:
the group R1 in formula III includes but is not limited to phenyl substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, the substituents include but are not limited to halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylmercapto, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl, etc.), heterocyclic substituents (including but not limited to furan ring, thiophene ring, pyridine ring, etc.), alkyl, etc.; the R2 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, etc.; the R3 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, and the like;
the R2 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, etc.; the R2 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, and the like; the R3 groups include, but are not limited to, phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including, but not limited to, halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.;
the R3 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, etc.; the R2 groups include, but are not limited to, phenyl, substituted phenyl (including mono-and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan, thiophene, pyridine, etc.), alkyl, and the like; the R3 groups include, but are not limited to, phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including, but not limited to, halo, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including, but not limited to, furan rings, thiophene rings, pyridine rings, etc.), alkyl, and the like.
A preparation method of beta-sulfonyl fluoroketone compounds shown in a formula I comprises the following steps:
step 1: adding alkyne, sulfonyl fluorine chloride, lithium perchlorate and ether into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is finished, the reaction solution is concentrated and then separated by column chromatography to obtain a target product;
the mol ratio of alkyne to sulfonyl fluoride chloride is 1: 2, the molar ratio of the lithium perchlorate to the lithium perchlorate is 1: 10, adding ethyl ether to form a solution with the concentration of 0.01M, wherein the used positive electrode material is a graphite flake, the used negative electrode material is a graphite flake, the set voltage is 20V, the reaction time is 12 hours, and the molar ratio of alkyne to sulfonyl fluorine chloride is 1: 0.1 to 1: 10, the molar ratio of alkyne to lithium perchlorate is in the range of 1: 0.1 to 1: 100, the ether can be replaced by other solvents, including but not limited to tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane, ethylene glycol monomethyl ether, etc., the solubility of the reaction solution formed is selected from 0.001M to 2M, the graphite flake of the electrode sheet material can be replaced by other materials, including but not limited to zinc metal, iron metal, nickel metal, copper metal, magnesium metal, aluminum metal, platinum metal, graphite felt, the voltage range is 1V to 36V, and the reaction time is 1 hour to 24 hours.
A preparation method of beta-sulfonyl fluoroketone and a compound shown in a formula II comprises the following steps:
step 1: adding alkyne, sulfonyl fluorine chloride, lithium perchlorate and tetrahydrofuran into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is finished, the reaction solution is concentrated and then separated by column chromatography to obtain the target product.
The mol ratio of alkyne to sulfonyl fluoride chloride is 1: 2, the molar ratio of the lithium perchlorate to the lithium perchlorate is 1: 10, adding ethyl ether to form a solution with the concentration of 0.01M, wherein the used positive electrode material is a graphite flake, the used negative electrode material is a graphite flake, the set voltage is 20V, the reaction time is 12 hours, and the molar ratio of alkyne to sulfonyl fluorine chloride is 1: 0.1 to 1: 10, the molar ratio of alkyne to lithium perchlorate is in the range of 1: 0.1 to 1: 100, the ether can be replaced by other solvents, including but not limited to tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane, ethylene glycol monomethyl ether, etc., the solubility of the reaction solution formed is selected from 0.001M to 2M, the graphite flake of the electrode sheet material can be replaced by other materials, including but not limited to zinc metal, iron metal, nickel metal, copper metal, magnesium metal, aluminum metal, platinum metal, graphite felt, the voltage range is 1V to 36V, and the reaction time is 1 hour to 24 hours.
A preparation method of a beta-sulfonyl fluoroketone derivative comprises the following steps:
step 1: adding beta-sulfonyl fluoroketone, hydrazine, acetonitrile and water into a reaction bottle, and stirring at room temperature;
step 2: after the reaction is finished, concentrating the reaction solution, and then carrying out column chromatography separation to obtain the target product.
The molar ratio of beta-sulfonyl fluoroketone to hydrazine is 1: 2, the ratio of acetonitrile to water is 1; 1, adding tetrahydrofuran and water to form a solution with the concentration of 0.1M and the reaction time of 24 hours;
the molar ratio of beta-sulfonyl fluoroketone to hydrazine ranges from 1: 0.1 to 1: 10, the ratio of acetonitrile to water is 1: 0.1 to 1: 10, the stirring temperature is 20 ℃ to 100 ℃, and the reaction time is 1 hour to 48 hours.
General experimental procedure:
A. synthesizing a compound represented by formula I:
alkyne (1eq), sulfonyl fluoride chloride (2eq), lithium perchlorate (10eq) and ether (0.01M) were added to a predried 25mL three-necked reaction flask. And (3) taking a magnesium sheet as an anode and an aluminum sheet as a cathode, connecting a power supply, setting the voltage to be 20V, stirring the reaction system at room temperature for 8 hours, concentrating the reaction solution after the reaction is finished, and separating by column chromatography to obtain the expected product.
B. Synthesizing a compound represented by formula II:
alkyne (1eq), sulfonyl fluoride chloride (3eq), lithium perchlorate (20eq) and tetrahydrofuran (0.01M) were added to a predried 25mL three-necked reaction flask. And (3) taking a magnesium sheet as an anode and an aluminum sheet as a cathode, switching in a power supply, setting the voltage to be 15V, stirring the reaction system at room temperature for 8 hours, concentrating the reaction solution after the reaction is finished, and separating by column chromatography to obtain the expected product.
C. Synthesizing a compound represented by formula III:
beta-sulfonylfluoroketone, hydrazine (2eq), acetonitrile (0.2M) and water (0.2M) were added to a reaction flask and stirred at 50 ℃ for 12 hours. After the reaction is finished, concentrating the reaction solution, and then carrying out column chromatography separation to obtain the target product.
Example 1:
the product 1a was obtained in 88% yield according to general experimental procedure a using the starting material p-tert-butylacetylene.
1H NMR(600MHz,CDCl3)δ7.91(d,J＝8.4Hz,2H),7.58(d,J＝8.4 Hz,2H),4.99(d,J＝2.0Hz,2H),1.38(s,9H).
13C NMR(150MHz,CDCl3)δ184.1,159.5,131.9(d,J＝2.6Hz),129.0, 126.3,57.3(d,J＝15.6Hz),35.5,31.0.
19F NMR(565MHz,CDCl3)δ62.8.
HRMS-ESI(m/z)[M-H]-calculated for C12H14FO3S 257.0653,found 257.0651.
Example 2:
using the starting 4-methyl-1-pentyne according to general experimental procedure A, the product 1b was obtained in 81% yield.
1H NMR(600MHz,CDCl3)δ4.39(d,J＝3.0Hz,2H),2.55(d,J＝6.8 Hz,2H),2.19(dp,J＝13.4,6.7Hz,1H),0.95(d,J＝6.7Hz,6H).
13C NMR(150MHz,CDCl3)δ194.5,60.6(d,J＝14.9Hz),52.2(d, J＝2.4Hz),24.3,22.3.
19F NMR(565MHz,CDCl3)δ61.8.
HRMS-ESI(m/z)[M-H]-calculated for C6H10FO3S 181.0340,found 181.0339.
Example 3:
the product 1c was obtained in 85% yield according to general experimental procedure a using the starting material phenylacetylene.
1H NMR(600MHz,CDCl3)δ7.96(dd,J＝8.4,1.2Hz,2H),7.73– 7.67(m,1H),7.59–7.53(m,2H),5.00(d,J＝2.3Hz,2H).
13C NMR(150MHz,CDCl3)δ184.9,135.4,134.6(d,J＝2.8Hz),129.4, 129.0,57.6(d,J＝15.8Hz).
19F NMR(565MHz,CDCl3)δ62.9.
HRMS-ESI(m/z)[M-H]-calculated for C8H6FO3S 201.0027,found 201.0027.
Example 4:
the starting material 3-ethynylthiophene was used to give product 1d in 61% yield according to general experimental procedure B.
1H NMR(600MHz,CDCl3)δ8.35(dd,J＝2.8,1.2Hz,1H),7.63(dd, J＝5.2,1.2Hz,1H),7.45(dd,J＝5.2,2.8Hz,1H),6.16(s,1H).
13C NMR(150MHz,CDCl3)δ176.8,136.9(d,J＝2.8Hz),136.8,128.0, 127.6,68.9(d,J＝18.7Hz).
19F NMR(565MHz,CDCl3)δ52.2.
HRMS-ESI(m/z)[M-H]-calculated for C6H3ClFO3S2 240.9202,found 240.9207.
Example 5:
according to general experimental procedure C, the product 1e was obtained in 70% yield using the starting materials β -sulfonyl fluoroacetophenone and p-toluenesulfonyl hydrazide.
1H NMR(600MHz,CDCl3)δ8.01(d,J＝8.4Hz,2H),7.58–7.53(m, 2H),7.50–7.46(m,1H),7.43(t,J＝7.4Hz,2H),7.35(d,J＝8.1 Hz,2H),4.33(s,2H),2.43(s,3H).
13C NMR(150MHz,CDCl3)δ148.8,146.3,133.0,132.1,130.1,129.7, 129.7,129.3,126.2,51.1,21.9.
HRMS-ESI(m/z)[M+Na]+calculated for C15H14N2NaO4S2 373.0287,found 373.0291.
Test example 1: the killing rate of the compound on nematodes is shown in figure 1
Nematodes were provided by the forest pathology laboratory of Nanjing forestry university.
1. Solution A is prepared according to the following proportion for standby. (100. mu.L acetone + 4900. mu.L 1 wt% SDS/H2O)
2. The compound was dissolved in solution a until use. (2mg/mL)
3. The compound solution and the nematode solution were mixed separately (100. mu.L + 100. mu.L), and the nematode killing rate was observed after standing for one hour, as shown in FIG. 1;
FIG. 2 is a diagram of: in the photograph of the nematode fluid treated in 1b, the nematodes died and appeared to be stiff.
FIG. 3 is a diagram of: in the photograph of the nematode fluid treated at 1c, the nematodes died and appeared to be stiff.
Test example 2: the inhibitory effect of the compounds on anthrax is shown in fig. 4 and 5.
Anthrax bacteria were provided by forest pathology laboratories of Nanjing forestry university.
1. The compound was dissolved in methanol until use. (2mg/mL)
2. The effect of the compounds on inhibiting the anthrax bacteria is primarily screened by a perforation method.
3. The inhibition effect of the compound on the anthrax bacteria is obtained preliminarily by comparing the size of the inhibition zone.
FIG. 4 is a diagram of: inhibitory effect of Compounds 1a-1c on anthrax bacteria. By comparison with the control group, the compounds 1a-1c have certain inhibitory effect on anthrax bacteria.
FIG. 5 is a diagram: inhibitory Effect of Compound 1d-1e on anthrax bacteria. Compared with a control group, the compound 1d has a certain inhibition effect on the anthrax bacteria, and the compound 1e has a better inhibition effect on the anthrax bacteria.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. The structure of the beta-sulfonyl fluoroketone is shown as the formula I and the formula II:
the R1 group in formula I includes, but is not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
the R2 group in formula I includes, but is not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
the R3 group in formula II includes but is not limited to phenyl, substituted phenyl, heterocyclic substituent, alkyl, halogen.
2. The structure of a beta-sulfonyl fluoroketone derivative is shown as a formula III:
the R1 group in formula III includes, but is not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
r2 groups include, but are not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl;
the R3 groups include, but are not limited to, phenyl, substituted phenyl, heterocyclic substituents, alkyl, halo, and the like.
3. The preparation method of the beta-sulfonyl fluoroketone compound shown in the formula I in the claim 1, which comprises the following steps:
step 1: adding alkyne, sulfonyl fluorine chloride, lithium perchlorate and ether into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is finished, the reaction solution is concentrated and then separated by column chromatography to obtain the target product.
4. The method for preparing the beta-sulfonyl fluoroketone compound shown in the formula II according to claim 1, which comprises the following steps:
step 1: adding alkyne, sulfonyl fluorine chloride, lithium perchlorate and tetrahydrofuran into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is finished, the reaction solution is concentrated and then separated by column chromatography to obtain the target product.
5. The preparation method of the beta-sulfonyl fluoroketone derivative according to claim 2, comprising the following steps:
step 1: adding beta-sulfonyl fluoroketone, hydrazine, acetonitrile and water into a reaction bottle, and stirring at room temperature;
step 2: after the reaction is finished, concentrating the reaction solution, and then carrying out column chromatography separation to obtain the target product.
6. The preparation method of the beta-sulfonyl fluoroketone compound shown in the formula I in claim 4, which is characterized in that: the molar ratio of alkyne to sulfonyl fluoride chloride is in the range of 1: 0.1 to 1: 10, the molar ratio of alkyne to lithium perchlorate is in the range of 1: 0.1 to 1: 100, the ether can be replaced by other solvents, including but not limited to tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane and ethylene glycol monomethyl ether, the solubility of the formed reaction liquid is selected from 0.001M to 2M, the graphite flake of the electrode sheet material can be replaced by other materials, including but not limited to zinc metal, iron metal, nickel metal, copper metal, magnesium metal, aluminum metal, platinum metal and graphite felt, the voltage range is 1V to 36V, and the reaction time is 1 hour to 24 hours.
7. The method for preparing β -sulfonyl fluoroketone derivatives according to claim 1, wherein: the molar ratio of beta-sulfonyl fluoroketone to hydrazine ranges from 1: 0.1 to 1: 10, the ratio of acetonitrile to water is 1: 0.1 to 1: 10, the stirring temperature is 20 ℃ to 100 ℃, and the reaction time is 1 hour to 48 hours.
8. The method for preparing the beta-sulfonyl fluoroketone compound shown in the formula II according to claim 1, which is characterized in that: the molar ratio of alkyne to sulfonyl fluoride chloride is in the range of 1: 0.1 to 1: 10, the molar ratio of alkyne to lithium perchlorate is in the range of 1: 0.1 to 1: 100, the ether can be replaced by other solvents, including but not limited to tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane and ethylene glycol monomethyl ether, the solubility of the formed reaction liquid is selected from 0.001M to 2M, the graphite flake of the electrode sheet material can be replaced by other materials, including but not limited to zinc metal, iron metal, nickel metal, copper metal, magnesium metal, aluminum metal, platinum metal and graphite felt, the voltage range is 1V to 36V, and the reaction time is 1 hour to 24 hours.
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