CN113666852B - 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
- Publication number
- CN113666852B CN113666852B CN202111036532.7A CN202111036532A CN113666852B CN 113666852 B CN113666852 B CN 113666852B CN 202111036532 A CN202111036532 A CN 202111036532A CN 113666852 B CN113666852 B CN 113666852B
- Authority
- CN
- China
- Prior art keywords
- sulfonyl
- beta
- fluoroketone
- substituted phenyl
- alkyne
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/78—Halides of sulfonic acids
- C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
- C07C309/81—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
- A01N41/08—Sulfonic acid halides; alpha-Hydroxy-sulfonic acids; Amino-sulfonic acids; Thiosulfonic acids; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/10—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with sulfur as the ring hetero atom
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/78—Halides of sulfonic acids
- C07C309/79—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms
- C07C309/80—Halides of sulfonic acids having halosulfonyl groups bound to acyclic carbon atoms of a saturated carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/06—1,2,3-Thiadiazoles; Hydrogenated 1,2,3-thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/18—Radicals substituted by singly bound hetero atoms other than halogen by sulfur atoms
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses beta-sulfonyl fluoroketone and derivatives thereof, and a preparation method thereof, and experiments prove that the beta-sulfonyl fluoroketone and derivatives thereof have good nematode killing effect, the beta-sulfonyl fluoroketone and derivatives thereof have good anthrax bacteria inhibiting effect, the beta-sulfonyl fluoroketone and derivatives thereof have simple structure, low cost and wide application prospect, and the synthesis method thereof takes alkyne and sulfonyl fluoride chloride as raw materials under the electrochemical condition, and the target compound is obtained through free radical reaction, 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.
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 nematodiasis, also known as "cancer of pine wood". This condition is caused by pine nematodes and can cause significant economic losses. Since the first discovery in the last century, pine nematodiasis has developed into a global pine crisis. Meanwhile, for the control of nematodes, anthrax is called eighth important plant pathogenic fungi, which have a great threat to tropical fruit trees, fir and the like, and cause high loss each year. Therefore, the research and development of novel medicines for preventing and treating nematodes and anthrax bacteria has important value, and at present, the synthesis method of beta-sulfonyl fluoroketone only has one report, about 4 steps are needed, and the yield is very low, so the research and development of a suitable synthesis method of beta-sulfonyl fluoroketone has become the research subject to be solved urgently at present, and the preparation method and application of beta-sulfonyl fluoroketone and derivatives thereof are brought.
Disclosure of Invention
The technical problem 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 above purpose, the present invention provides the following technical solutions:
beta-sulfonyl fluoroketone has a structure shown in a formula I and a formula II:
the R1 group in the formula I comprises phenyl, substituted phenyl, heterocyclic substituent and alkyl;
the R2 group in the formula I comprises phenyl, substituted phenyl, heterocyclic substituent and alkyl;
the R3 group in formula II includes phenyl, substituted phenyl, heterocyclic substituent and alkyl.
The structure of the beta-sulfonyl fluoro ketone derivative is shown as a formula III:
the R1 group in the formula III comprises phenyl, substituted phenyl, heterocyclic substituent and alkyl;
r2 groups include phenyl, substituted phenyl, heterocyclic substituents, alkyl;
the R3 group includes phenyl, substituted phenyl, heterocyclic substituents, and alkyl.
The preparation method of the beta-sulfonyl fluoroketone compound shown in the formula I comprises the following steps:
step 1: adding alkyne, sulfonyl fluoride chloride, lithium perchlorate and diethyl ether into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is stirred, concentrating the reaction solution, and separating by column chromatography to obtain a target product;
the preparation method of the beta-sulfonyl fluoroketone compound shown in the formula II comprises the following steps:
step 1: adding alkyne, sulfonyl fluoride 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 stirred, the reaction solution is concentrated, and then the target product is obtained through column chromatography separation.
The preparation method of the beta-sulfonyl fluoro ketone derivative comprises the following steps:
step 1: adding beta-sulfonyl fluoride ketone, hydrazine, acetonitrile and water into a reaction bottle, and stirring at room temperature;
step 2: after the reaction is finished, concentrating the reaction liquid, and separating by column chromatography to obtain a target product.
Preferably, the molar ratio of alkyne to sulfonyl fluoride chloride ranges from 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, diethyl ether can be replaced by other solvents including tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane and ethylene glycol monomethyl ether, the solubility of the formed reaction liquid ranges from 0.001M to 2M, and the electrode plate material graphite flake can be replaced by other materials including metallic zinc, metallic iron, metallic nickel, metallic copper, metallic magnesium, metallic aluminum, metallic platinum and graphite felt, the voltage ranges from 1V to 36V, and the reaction time ranges from 1 hour to 24 hours.
Preferably, the molar ratio of β -sulfonyl fluoroketone to hydrazine is in the range of 1:0.1 to 1:10, acetonitrile to water ratio is 1:0.1 to 1:10, stirring temperature is 20-100 ℃, and reaction time is 1-48 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, alkyne and sulfonyl fluoride chloride are used as raw materials under an electrochemical condition, and the target compound is obtained through free radical reaction, 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. the test proves that the beta-sulfonyl fluoroketone and the derivative thereof have good effect of killing nematodes, and the beta-sulfonyl fluoroketone and the derivative thereof have good effect of inhibiting anthrax bacteria, and the beta-sulfonyl fluoroketone and the derivative thereof have simple structure, low cost and wide application prospect.
Drawings
FIG. 1 is a table showing the killing rate of test example 1 according to the present invention;
FIG. 2 is a photograph of a nematode solution treated in test example 1 of the present invention with 1 b;
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-1c of test example 2 of the present invention on anthrax;
FIG. 5 shows the inhibitory effect of Compounds 1d to 1e of test example 2 of the present invention on anthrax.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a technical scheme that: beta-sulfonyl fluoroketone has a structure shown in a formula I and a formula II:
the R1 group in the formula I comprises phenyl, substituted phenyl (comprising mono-substituted phenyl and multi-substituted phenyl, wherein the substituent comprises halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methyl mercapto, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl and the like), heterocyclic substituent (comprising furan ring, thiophene ring, pyridine ring and the like), alkyl and the like; r2 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; r3 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.;
the R2 group in the formula I comprises phenyl, substituted phenyl (comprising mono-substituted phenyl and multi-substituted phenyl, wherein the substituent comprises halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methyl mercapto, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl and the like), heterocyclic substituent (comprising furan ring, thiophene ring, pyridine ring and the like), alkyl and the like; r2 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; r3 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.;
the R3 group in the formula II comprises phenyl, substituted phenyl (comprising mono-substituted phenyl and multi-substituted phenyl, and the substituents comprise halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl and the like), heterocyclic substituent (comprising furan ring, thiophene ring, pyridine ring and the like), alkyl and the like; r2 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; the R3 group includes phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan ring, thiophene ring, pyridine ring, etc.), alkyl.
The structure of the beta-sulfonyl fluoro ketone derivative is shown as a formula III:
the R1 group in the formula III comprises phenyl substituted phenyl (including monosubstituted phenyl and polysubstituted phenyl, and substituents comprise halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxyl, alkenyl, alkynyl and the like), heterocyclic substituents (including furan ring, thiophene ring, pyridine ring and the like), alkyl and the like; r2 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; r3 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.;
r2 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; r2 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; r3 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.;
r3 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; r2 groups include phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan rings, thiophene rings, pyridine rings, etc.), alkyl, etc.; the R3 group includes phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, carbonyl, ester, aldehyde, nitro, trifluoromethyl, trifluoromethoxy, methylthio, alkyl, methoxy, dimethylamino, hydroxy, alkenyl, alkynyl, etc.), heterocyclic substituents (including furan ring, thiophene ring, pyridine ring, etc.), alkyl.
The preparation method of the beta-sulfonyl fluoroketone compound shown in the formula I comprises the following steps:
step 1: adding alkyne, sulfonyl fluoride chloride, lithium perchlorate and diethyl ether into a three-neck flask, inserting an electrode plate, switching on a power supply, and setting voltage;
step 2: after the reaction is stirred, concentrating the reaction solution, and separating by column chromatography to obtain a target product;
the molar ratio of alkyne to sulfonyl fluoride chloride is 1:2, the molar ratio of the lithium perchlorate to the lithium perchlorate is 1:10, the concentration of the solution formed after diethyl ether is 0.01M, the anode electrode material is graphite flake, the cathode electrode material is graphite flake, the set voltage is 20V, the reaction time is 12 hours, and the molar ratio of alkyne to sulfonyl fluoride 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, diethyl ether can be replaced by other solvents including tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane, ethylene glycol monomethyl ether and the like, the solubility of the formed reaction liquid ranges from 0.001M to 2M, the electrode plate material graphite flake can be replaced by other materials including metallic zinc, metallic iron, metallic nickel, metallic copper, metallic magnesium, metallic aluminum, metallic platinum and graphite felt, the voltage ranges from 1V to 36V, and the reaction time ranges from 1 hour to 24 hours.
The preparation method of the beta-sulfonyl fluoroketone compound shown in the formula II comprises the following steps:
step 1: adding alkyne, sulfonyl fluoride 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 stirred, the reaction solution is concentrated, and then the target product is obtained through column chromatography separation.
The molar ratio of alkyne to sulfonyl fluoride chloride is 1:2, the molar ratio of the lithium perchlorate to the lithium perchlorate is 1:10, the concentration of the solution formed after diethyl ether is 0.01M, the anode electrode material is graphite flake, the cathode electrode material is graphite flake, the set voltage is 20V, the reaction time is 12 hours, and the molar ratio of alkyne to sulfonyl fluoride 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, diethyl ether can be replaced by other solvents including tetrahydrofuran, acetonitrile, 1, 4-dioxane, N-dimethylformamide, dichloromethane, ethylene glycol monomethyl ether and the like, the solubility of the formed reaction liquid ranges from 0.001M to 2M, the electrode plate material graphite flake can be replaced by other materials including metallic zinc, metallic iron, metallic nickel, metallic copper, metallic magnesium, metallic aluminum, metallic platinum and graphite felt, the voltage ranges from 1V to 36V, and the reaction time ranges from 1 hour to 24 hours.
The preparation method of the beta-sulfonyl fluoro ketone derivative comprises the following steps:
step 1: adding beta-sulfonyl fluoride ketone, hydrazine, acetonitrile and water into a reaction bottle, and stirring at room temperature;
step 2: after the reaction is finished, concentrating the reaction liquid, and separating by column chromatography to obtain a target product.
The molar ratio of the beta-sulfonyl fluoride ketone to the 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 is in the range of 1:0.1 to 1:10, acetonitrile to water ratio is 1:0.1 to 1:10, stirring temperature is 20-100 ℃, and reaction time is 1-48 hours.
General experimental procedure:
A. synthesizing a compound represented by formula I:
alkyne (1 eq), sulfonyl fluoride chloride (2 eq), lithium perchlorate (10 eq) and diethyl ether (0.01M) were added to a previously dried 25mL three port reaction flask. And (3) taking a magnesium sheet as an anode, taking an aluminum sheet as a cathode, accessing 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 (1 eq), sulfonyl fluoride chloride (3 eq), lithium perchlorate (20 eq) and tetrahydrofuran (0.01M) were added to a previously dried 25mL three-port reaction flask. And (3) taking a magnesium sheet as an anode, taking an aluminum sheet as a cathode, accessing 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-sulfonyl fluoroketone, hydrazine (2 eq), acetonitrile (0.2M) and water (0.2M) were added to the reaction flask and stirred for 12 hours at 50 ℃. After the reaction is finished, concentrating the reaction liquid, and separating by column chromatography to obtain a target product.
Example 1:
according to general experimental procedure a, using the starting material p-tert-butylphenylacetylene, product 1a is obtained in 88% yield.
1 H NMR(600MHz,CDCl3)δ7.91(d,J＝8.4Hz,2H),7.58(d,J＝8.4Hz,2H),4.99(d,J＝2.0Hz,2H),1.38(s,9H).
13 C 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.
19 F NMR(565MHz,CDCl3)δ62.8.
HRMS-ESI(m/z)[M-H]-calculated for C12H14FO3S 257.0653,found257.0651.
Example 2:
according to general experimental procedure a, starting material 4-methyl-1-pentyne was used to give product 1b in 81% yield.
1 H NMR(600MHz,CDCl3)δ4.39(d,J＝3.0Hz,2H),2.55(d,J＝6.8Hz,2H),2.19(dp,J＝13.4,6.7Hz,1H),0.95(d,J＝6.7Hz,6H).
13 C NMR(150MHz,CDCl3)δ194.5,60.6(d,J＝14.9Hz),52.2(d,J＝2.4Hz),24.3,22.3.
19 F NMR(565MHz,CDCl3)δ61.8.
HRMS-ESI(m/z)[M-H]-calculated for C6H10FO3S 181.0340,found 181.0339.
Example 3:
according to general experimental procedure a, using the starting phenylacetylene to give product 1c in 85% yield.
1 H 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).
13 C NMR(150MHz,CDCl3)δ184.9,135.4,134.6(d,J＝2.8Hz),129.4,129.0,57.6(d,J＝15.8Hz).
19 F NMR(565MHz,CDCl3)δ62.9.
HRMS-ESI(m/z)[M-H]-calculated for C8H6FO3S 201.0027,found 201.0027.
Example 4:
according to general experimental procedure B, starting 3-ethynyl thiophene is used to give product 1d in 61% yield.
1 H 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).
13 C NMR(150MHz,CDCl3)δ176.8,136.9(d,J＝2.8Hz),136.8,128.0,127.6,68.9(d,J＝18.7Hz).
19 F 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, using the starting material β -sulfonylfluoro acetophenone with p-toluenesulfonyl hydrazide, product 1e was obtained in 70% yield.
1 H 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＝8.1Hz,2H),4.33(s,2H),2.43(s,3H).
13 C 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 to the nematodes is shown in figure 1
Nematodes are provided by the forest pathology laboratory at the university of Nanjing forestry.
1. Solution a was prepared for use as follows. (100. Mu.L of acetone+4900. Mu.L of 1wt% SDS/H2O)
2. The compound was dissolved in solution a for use. (2 mg/mL)
3. The compound solutions were mixed with the nematode solution (100. Mu.L+100. Mu.L), respectively, and after standing for one hour, the nematode killing rate was observed, as shown in FIG. 1;
fig. 2 is: in the photographs of the nematode liquid treated by the method 1b, nematodes are dead and are in a stiff state.
Fig. 3 is: in the photographs of the nematode liquid treated by the method 1c, nematodes are dead and are in a stiff state.
Test example 2: the inhibitory effect of the compounds on anthrax is shown in fig. 4 and 5.
Anthrax is provided by the forest pathology laboratory at the university of Nanjing forestry.
1. The compound was dissolved in methanol for use. (2 mg/mL)
2. And (3) primarily screening the effect of inhibiting anthrax by using a perforation method.
3. The inhibition effect of the compound on the anthrax bacteria is primarily obtained by comparing the sizes of the inhibition zones.
Fig. 4 is: inhibitory Effect of Compounds 1a-1c on anthrax. By comparison with the control group, the compounds 1a-1c have a certain inhibition effect on anthrax.
Fig. 5 is: inhibitory Effect of Compounds 1d-1e on anthrax. Compared with a control group, the compound 1d has a certain inhibition effect on the anthrax, and the compound 1e has a better inhibition effect on the anthrax.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (2)
1. A method for preparing beta-sulfonyl fluoride ketone shown in formulas 1a, 1b and 1c,
step 1: adding raw materials of alkyne, sulfonyl fluoride chloride, lithium perchlorate and diethyl ether into a three-neck flask, inserting an electrode plate, switching on a power supply, setting voltage, and setting the molar ratio of the raw materials of alkyne to sulfonyl fluoride chloride to be 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; using a magnesium sheet as an anode and an aluminum sheet as a cathode, wherein the voltage range is 1V to 36V, and the reaction time is 1 hour to 24 hours;
the raw material alkyne is p-tert-butyl phenylacetylene, 4-methyl-1-pentyne and phenylacetylene;
step 2: after the reaction is stirred, the reaction solution is concentrated, and then the target product is obtained through column chromatography separation.
2. A preparation method of beta-sulfonyl fluoroketone shown in a formula 1d,
step 1: adding 3-ethynyl thiophene, sulfonyl fluoride chloride, lithium perchlorate and tetrahydrofuran into a three-neck flask, inserting an electrode plate, switching on a power supply, setting voltage, and setting the molar ratio of 3-ethynyl thiophene to sulfonyl fluoride chloride to be 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, using a magnesium sheet as an anode and an aluminum sheet as a cathode; the voltage is 1V to 36V, and the reaction time is 1 hour to 24 hours;
step 2: after the reaction is stirred, the reaction solution is concentrated, and then the target product is obtained through column chromatography separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111036532.7A CN113666852B (en) | 2021-09-06 | 2021-09-06 | Preparation method and application of beta-sulfonyl fluoroketone and derivative thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111036532.7A CN113666852B (en) | 2021-09-06 | 2021-09-06 | Preparation method and application of beta-sulfonyl fluoroketone and derivative thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113666852A CN113666852A (en) | 2021-11-19 |
| CN113666852B true CN113666852B (en) | 2023-05-26 |
Family
ID=78548397
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111036532.7A Active CN113666852B (en) | 2021-09-06 | 2021-09-06 | Preparation method and application of beta-sulfonyl fluoroketone and derivative thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113666852B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114716352A (en) * | 2022-03-31 | 2022-07-08 | 南京林业大学 | Beta-ketosulfonyl fluoride compound, and preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174855B (en) * | 2020-11-16 | 2021-09-24 | 福州大学 | Preparation method of sulfonyl fluoride product |
| CN113248444B (en) * | 2021-05-31 | 2022-07-19 | 福州大学 | Fluorosulfonyl radical reagent and preparation method and application thereof |
-
2021
- 2021-09-06 CN CN202111036532.7A patent/CN113666852B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113666852A (en) | 2021-11-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113666852B (en) | Preparation method and application of beta-sulfonyl fluoroketone and derivative thereof | |
| CN110616439B (en) | Method for synthesizing 4-sulfonic acid substituted isoquinolone derivative through electrochemical oxidation | |
| Zhang et al. | Copper-catalyzed synthesis of 2, 2-difluoro-1, 3-benzoxathioles (selenoles) and their insecticidal activities: the selenium effect | |
| CN110453242B (en) | Method for electrochemically synthesizing rutaecarpine | |
| CN112778317B (en) | Synthetic method of [1,2,4] triazolo [1,5-a ] pyrimidine compound | |
| CN114605265B (en) | Acanthol and its synthesis process | |
| CN110511193A (en) | A kind of α -one thioamide analog compound and its synthetic method | |
| SU664568A3 (en) | Method of obtaining acyl-derivatives of erythromycinoxime | |
| CN109734667B (en) | Polysubstituted imidazole compound and synthesis method and application thereof | |
| CN108947995B (en) | Preparation method of polysubstituted oxadiazine derivative | |
| CN108503572B (en) | Synthetic method of 3-acyl pyrrole compound | |
| US4421923A (en) | Ring substituted crown ethers and method of producing same | |
| CN111116506B (en) | Synthesis method of arylmercapto diazole derivative | |
| CN110698422A (en) | Synthetic method of aromatic mercapto-diazole derivative | |
| CN114790172B (en) | Synthesis method for promoting 4-selenopyrazoles by using visible light | |
| CN110804010B (en) | Synthetic method of isatin derivative | |
| CN112126941B (en) | Polysubstituted 10-hydroxy phenanthrene derivative and preparation method thereof | |
| US4544766A (en) | Process for preparing aryl acetic acid derivatives | |
| CN107474001B (en) | synthetic method of α -diacetoxymethyl substituted nitrogen heterocyclic compounds | |
| CN114411182B (en) | Method for synthesizing alpha-carbonyl sulfoxide ylide dichlorides under electrocatalytic action | |
| SU740749A1 (en) | Method of preparing cyclohexylammonium salt of triphosphoinositide | |
| CN115725988A (en) | Electrochemical method for synthesizing spiroisoxazoline | |
| SU791749A1 (en) | Method of preparing derivatives of 2,5-dihydro-1h-1,5-benzodiazepins | |
| HU202491B (en) | Process for producing pyrroline derivatives | |
| CN115322127A (en) | Nitrogen-containing beta-ketosulfone compound and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |