CN105646298A - 2-oxo-, 2-hydroxyl and 2-acyloxy-2-substituted phenyl ethyl sulfonamide compound and preparation method and application thereof as bactericide - Google Patents
2-oxo-, 2-hydroxyl and 2-acyloxy-2-substituted phenyl ethyl sulfonamide compound and preparation method and application thereof as bactericide Download PDFInfo
- Publication number
- CN105646298A CN105646298A CN201610140209.7A CN201610140209A CN105646298A CN 105646298 A CN105646298 A CN 105646298A CN 201610140209 A CN201610140209 A CN 201610140209A CN 105646298 A CN105646298 A CN 105646298A
- Authority
- CN
- China
- Prior art keywords
- iii
- compound
- oxo
- phenyl ethyl
- substituted
- 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.)
- Granted
Links
- 0 CC(*C(CCCC1)C1=O)c(c(C(F)(F)F)c1)ccc1Cl Chemical compound CC(*C(CCCC1)C1=O)c(c(C(F)(F)F)c1)ccc1Cl 0.000 description 3
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
-
- 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
- A01N41/06—Sulfonic acid amides
-
- 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
- A01N43/08—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 oxygen 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/38—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reaction of ammonia or amines with sulfonic acids, or with esters, anhydrides, or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/36—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids
- C07C303/40—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of amides of sulfonic acids by reactions not involving the formation of sulfonamide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/80—Acids; Esters in position 3
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/68—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (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)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention provides novel 2-oxo-, 2-hydroxyl and 2-acyloxy-2-substituted phenyl ethyl sulfonamide compound and a synthetic method and application thereof as a bactericide. The method comprises: preparing 2-oxo-2-substituted phenyl ethyl potassium sulfonate (II) from substituted phenylethanone (I), 1,2-dichloroethane, sulfur trioxide.dioxane complex and potassium carbonate, dropwise adding a reaction solution of the 2-oxo-2-substituted phenyl ethyl potassium sulfonate, anhydrous dichloromethane, DMF and oxalyl chloride at room temperature into 2-trifluoromethyl-4-chloroaniline to obtain 2-oxo-2-substituted phenyl ethyl sulfonamide (III), subjecting the compound II to carbonyl reduction under certain conditions to obtain 2-hydroxyl-2-substituted phenyl ethyl sulfonamide (IV), and docking the compound IV further to acyl chlorides of various substitution types obtained by synthesis to synthesize novel serial compounds of 2-acyloxy-substituted phenyl ethyl sulfonamide. The compounds III, IV and V are very inhibitory for various Botrytis cinerea and pathogenic bacteria such as Thanatephorus cucumeris, Phyricularia oryzae, Phyricularia oryzae, Pythium aphanidermatum, Fusarium oxysporum f.sp.cucumerinum, Phytophthora capsici and Pseudopeziza medicaginis; the serial compounds III, IV and V are shown in a following general formula.
Description
Technical field
The present invention relates to the synthesis containing 2-oxo, 2-hydroxyl and 2-acyloxy-2-substituted-phenyl b-sulfonamide compound and the purposes as antibacterial, belong to field of agrochemicals.
Background technology
The application in disinfectant use in agriculture of the novel naphthene sulfamide aminated compounds originates from the full seminar of kingly way in the 2-oxo cyclo-dodecyl sulfamide compound (Wang Xiaoping of report in 1997; kingly way is complete. SCI; 1997; 18 (6): 889-893), fusarium graminearum Gibberllazeae and pear cucumerinum Venturianashicola is had better inhibitory activity by it. On Research foundation subsequently, candidate novel fungicides agent Hexanaphthene flusulfamide A (exploitation code name CAUWL-2004-L-13) is developed (CN1900059A; CN101720764A), can be used for preventing and treating the diseases such as graw mold of tomato, sclerotinia rot of colza, Cucumber Target Leaf Spot and scab. Within 2008, we report 14 N-substituted phenyl-2-oxo-2-phenyl ethyl sulfonamide compounds B (Li Xinghai; Deng. the synthesis of benzoyl Methanesulfomide and bactericidal activity. Pesticide Science journal; 2008,10 (2): 136-140) there is more excellent bactericidal activity. Utilize combinational chemistry to synthesize again 105 N-on this basis and replace-2-oxo-2-phenyl ethyl sulfonamide compounds C, compared with systematic research, on N, substituent group is bactericidal activity structure activity relationship (Li Xinghai when monosubstituted aniline, polysubstituted aniline, alpha substituted benzylamine and alkylamine, Deng .2-oxo-2-phenyl b-sulfonamide compound combinatorial compound and bactericidal activity research, Pesticide Science journal, 2016,18 (1): 28-36).
Summary of the invention
It is an object of the invention on the basis of 2-oxo-2-phenyl ethyl sulfonamide; with the 2-oxo-2-substituted-phenyl b-sulfonamide compound III of different substituents on synthesis phenyl ring; 2-hydroxyl-2-substituted-phenyl b-sulfonamide compound IV will be obtained after the carbonyl reduction of 2-position; acylation reaction synthesis 2-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide series compound V is carried out further with dissimilar acyl chlorides.Compound II per I, IV, V have good bactericidal activity.
Its concrete structure formula is as follows:
III-1��III-20:III-1:R1=3,4-(F)2; III-2:R1=3-Cl; III-3:R1=4-Cl; III-4:R1=2,4-(Cl)2; III-5:R1=4-Br; III-6:R1=2-CH3; III-7:R1=4-NO2; III-8:R1=3,5-(CF3)2; III-9:R1=4-F-3-CF3,III-10:R1=2,4-(Cl)2-5-F; III-11:R1=4-OCH3; III-12:R1=2-Cl; III-13:R1=2-Cl-3-F; III-14:R1=2-CF3; III-15:R1=3,5-(F)2; III-16:R1=4-CF3; III-17:R1=2-F; III-18:R1=2-NO2; III-19:R1=3-F; III-20:R1=3-CF3��
IV-1��IV-5:IV-1:R1=H; IV-2:R1=3-F;IV-3:R1=4-NO2; IV-4:R1=3,4-(F)2; IV-5:R1=3,5-(F)2. V-1��V-20:R1=3,5-(F)2;
V-1:R2=C2H5; V-2:R2=CH3; V-3:R2=3-pyridine radicals; V-4:R2=2-furyl; V-5:R2=2-ClC6H4; V-6:R2=3-FC6H4; V-7:R2=2-FC6H4; V-8:R2=CCl3; V-9:R2=CHCl2; V-10:R2=3-CH3C6H4; V-11:R2=2-CH3C6H4; V-12:R2=3-CF3C6H4; V-13:R2=2-CF3C6H4; V-14:R2=3-ClC6H4; V-15:R2=CH3CH2OCH2; V-16:R2=CH3(CH2)2CH2; V-17:R2=ClCH2CH2; V-18:R2=2,4-(CH3)2C6H3; V-19:R2=4-CH3C6H4; V-20:R2=4-OCH3C6H4;
Synthetic route is as follows:
Compound II per I, IV, V are to multiple botrytis cinerea, and rice banded sclerotial blight, Oryza sativa L. rice blast, the big speckle of Semen Maydis, melon and fruit corruption are mould, cereal reaping hook, Phytophthora capsici, Fructus Cucumidis sativi brown patch, Fructus Cucumidis sativi reaping hook, the rotten mould pathogen of melon and fruit growth have inhibitory action, for the preventing and treating of disease.
Detailed description of the invention
The synthesis of example 1.2-oxo-2-substituted-phenyl b-sulfonamide compound (III)
2-oxo-2-substituted-phenyl ethyl sulfonic acid potassium salt (II) is synthesized according to the method for list of references. List of references: Li Xinghai, Qi Zhiqiu, Zhong Changji, Zhang Yang, Ji Mingshan, Wang Yingzi, kingly way is complete. the synthesis of benzoyl Methanesulfomide and bactericidal activity. and Pesticide Science journal, 2008,10 (2): 136-140.
Under room temperature, 2-oxo-2-substituted-phenyl ethyl sulfonic acid potassium salt 0.01mol, anhydrous methylene chloride 40mL and DMF 0.2mL are added in 100mL there-necked flask, stir 10min, add oxalyl chloride 0.0114mol, react 3h. It is transferred to separatory funnel, washs with 10mL frozen water, separatory, dichloromethane layer is collected in conical flask, add anhydrous magnesium sulfate ,-20 DEG C of cold drying 20min in refrigerator. Sucking filtration obtains the dichloromethane solution of sulfonic acid chloride, is transferred in Dropping funnel by filtrate standby.
Adding 2-trifluoromethyl-4-chloroaniline 0.0052mol, triethylamine 0.0114mol, anhydrous methylene chloride 20mL in another 100mL there-necked flask, ice-water bath is cooled to 0 DEG C. The chloride solution that in dropping, step reaction prepares, controls temperature < 5 DEG C. After dropwising, naturally it is warmed up to room temperature and continues stirring 3h. Gained solution is proceeded to separatory funnel, after washing with the hydrochloric acid 15mL, saturated sodium bicarbonate 15mL, saturated aqueous common salt 15mL of 3mol/L successively, then dries with anhydrous sodium sulfate. Sucking filtration, concentrating under reduced pressure obtains crude product, obtains sterling through purification by silica gel column chromatography. Calculated yield, measures melting range, and carries out Structural Identification with nuclear magnetic resonance, NMR, infrared spectrum.
It is synthetically derived 2-oxo-2-substituted-phenyl ethyl sulfonamide compounds (III) totally 20 according to above-mentioned method.The physicochemical data of compound is in Table 1, and spectral data is in Table 2.
The yield of table 12-oxo-2-substituted-phenyl ethyl sulfonamide compounds (III), fusing point and states of matter
The nuclear-magnetism of table 22-oxo-2-substituted-phenyl ethyl sulfonamide compounds (III) and infrared data
The synthesis of example 2.2-hydroxyl-2-substituted-phenyl ethyl sulfonamide compounds (IV)
Room temperature, by 2-oxo-2-substituted-phenyl b-sulfonamide compound (III) 0.005mol under nitrogen protection, methanol 20mL joins in the there-necked flask of 100mL, is slowly added dropwise 0.32gNaBH4+ 6mL1% sodium hydroxide+6mLCH3The sodium borohydride solution that OH is made into, 30min dropwises, stirring reaction 1h. After reactant liquor concentrating under reduced pressure, it is added thereto to 50mL ethyl acetate and 20mL water, separatory, ethyl acetate layer is respectively with 1% dilute hydrochloric acid 15mL and 15mL water washing, dried with anhydrous sodium sulfate, sucking filtration, filtrate reduced in volume reduced after crude product 2-hydroxyl-2-substituted-phenyl ethyl sulfonamide compounds (IV). Obtain sterling, calculated yield by purification by silica gel column chromatography, measure fusing point, and carry out Structural Identification with nuclear magnetic resonance, NMR, infrared spectrum.
It is synthetically derived 2-hydroxyl-2-substituted-phenyl ethyl sulfonamide compounds (IV) totally 5 according to above-mentioned method. The physicochemical data of compound is in Table 3, and spectral data is in Table 4.
The yield of table 32-hydroxyl-2-substituted-phenyl ethyl sulfonamide compounds (IV), fusing point and states of matter
The nuclear-magnetism of table 42-hydroxyl-2-substituted-phenyl b-sulfonamide compound (IV) and infrared data
The synthesis of example 3.2-acyloxy-2-(3,5-difluorophenyl) b-sulfonamide compound (V)
Under nitrogen protection, room temperature is by dry 20mLCH2Cl2, 0.001mol2-hydroxyl-2-(3,5-difluorophenyl) ethyl sulfonamide (IV-5), 0.1mLN, N, N ', N '-tetramethylethylenediamine (TMEDA), 1g molecular sieve successively add in 50mL there-necked flask, add acyl chlorides under stirring, continue stirring reaction 4h. Stirring 2 hours, sucking filtration, filtrate proceeds to separatory funnel, quickly with after the washing of frozen water 15mL �� 2, with the dry 10min of anhydrous sodium sulfate, sucking filtration, concentrating under reduced pressure obtains crude product, and column chromatography obtains sterling, calculated yield, surveys fusing point, and carries out Structural Identification with nuclear magnetic resonance, NMR, infrared spectrum.
2-acyloxy-2-(3, the 5-difluorophenyl) ethyl sulfonamide (V) being synthetically derived according to the method described above, totally 20. The physicochemical data of compound is in Table 5, and spectral data is in Table 6.
The yield of table 52-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide (V), fusing point, states of matter
The nuclear-magnetism of table 62-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide (V) and infrared data
The example 4. noval chemical compound (III, IV, V) bactericidal activity to ash arrhizus bacteria
With reference to farm-chemical indoor determination test rule, adopt Plating (suppressing mycelial growth experiment), by the pastille culture medium that concentration is 50 �� g/mL, measure the bactericidal activity of the target compound (III, IV, V) the multiple botrytis cinerea Botrytiscinerea to picking up from different regions. With procymidone for comparison medicament, arranging acetone solvent is blank, and each process is in triplicate. After the bacterium colony in blank fully grows, measure the colony diameter of each process with decussation method, take its meansigma methods, calculate suppression ratio by below equation:
Suppression ratio (%)=(blank colony diameter _ pastille medium colony diameter)/(blank colony diameter-bacterium cake diameter) �� 100%
First determining 2-oxo-2-substituted-phenyl b-sulfonamide compound (III) inhibitory activity to AS-12 (picking up from Anshan, liaoning Province), DD-15 (picking up from Dandong), DG-3 (picking up from Liaoning Donggang City), FS-06 (picking up from Fushun), HLD-16 (picking up from Liaoning Huludao City), LZ-4 (picking up from Liaozhong, Liaoning), PJ-10 (picking up from Liaoning Panjin) and SY-10 (picking up from Shenyang, Liaoning) 8 kinds of botrytis cinerea Botrytiscinerea, result of the test is in Table 7.Multiple ash arrhizus bacteria is all shown very high bactericidal activity by noval chemical compound III, the suppression ratio of most compounds has been above 80%, wherein having 9,8,14,6,4,0,14,1 compound suppression ratio to above 8 bacterial strains respectively higher than 90%, activity is higher than comparison medicament procymidone. The highest suppression ratio has respectively reached 96.2%, 92.8%, 99.2%, 96.4%, 93.7%, 81.4%, 94.8%, 92.9%.
Compound 2-hydroxyl-2-substituted-phenyl b-sulfonamide compound (IV) to CY-09 (picking up from Chaoyang), DL-11 (picking up from Dalian), HLD-15 (picking up from Huludao City) bacteriostatic activity in Table 8, multiple ash arrhizus bacteria is also shown very high bactericidal activity by it, most suppression ratio have reached more than 90%, activity is suitable with procymidone, and the highest suppression ratio has respectively reached 95.1%, 99.7%, 90.7%.
2-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide (V) to CY-09 and CY-14 (picking up from Chaoyang), DG-1 (picking up from Liaoning Donggang City), DL-11 (picking up from Dalian), FS-9 and FS-10 (picking up from Fushun), HLD-15 (picking up from Liaoning Huludao City) 7 kinds of botrytis cinerea Botrytiscinerea inhibitory activity in Table 9. Multiple ash arrhizus bacteria is shown very high bactericidal activity by noval chemical compound V, having 6,4,0,3,3,4,4 compounds activity to 7 kinds of grey mold bacterial strains respectively higher than comparison medicament procymidone, the highest suppression ratio is 91.8%, 95.3%, 80.1%, 90.6%, 89.2%, 89.2%, 90.4% respectively.
Table 72-oxo-2-substituted-phenyl b-sulfonamide compound (III) bactericidal activity (50 �� g/mL) to 8 kinds of ash arrhizus bacterias
Table 82-hydroxyl-2-substituted-phenyl b-sulfonamide compound (IV) bactericidal activity (50 �� g/mL) to 3 kinds of ash arrhizus bacterias
Table 92-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide (V) bactericidal activity (50 �� g/mL) to 7 kinds of ash arrhizus bacterias
The Concentraton gradient of ash arrhizus bacteria is measured by example 5. compound (III, IV, V)
With reference to farm-chemical indoor determination test rule, adopt Plating (suppressing mycelial growth experiment), sample compound is made g/mL5 original concentration of 10000,2500,625,156,39 �� with acetone respectively. Under aseptic condition, dilute 100 times of pastille culture medium obtaining 100,25,6.25,1.56,0.39 g/mL5 concentration of �� with PDA (potato dextrose medium). The truffle of inoculation diameter 5mm, cultivates 3-5 days at 23 �� 2 DEG C. Measure colony diameter (decussation method). Utilize EXCEL computed in software EC50Value, comparative compound virulence size.
2-oxo-2-substituted-phenyl ethyl sulfonamide compounds the III EC to SY-10 (picking up from Shenyang, Liaoning) and DD-15 (picking up from Dandong) 2 kinds of ash arrhizus bacteria Botrytiscinerea50In Table 10. Toxicity test result shows that 2 kinds of grey mold pathogen are had significantly high bactericidal activity by 8 2-oxo-2-substituted-phenyl b-sulfonamide compounds. From EC50Value is seen, the activity of ash arrhizus bacteria SY-10 is above comparison medicament procymidone by Compound II per I-1, III-13, III-15, relative virus force multiple respectively 2.1,3.9,3.3, compared with control compound B-1 (N-(2-trifluoromethyl-4-chlorophenyl)-2-oxo-2-phenyl ethyl sulfonamide), relative virus force multiple respectively 3.3,6.2,5.3. The activity of ash arrhizus bacteria DD-15 is above comparison medicament of pyrimethanil by 8 compounds, relative virus force multiple is all more than 13.8 times, the activity of ash arrhizus bacteria DD-15 is above control compound B-1 by 7 compounds, and the relative virus force multiple that wherein Compound II per I-2 and III-15 and B-1 compares is 3.6 and 3.1 respectively.
Compound 2-hydroxyl-2-substituted-phenyl b-sulfonamide compound (IV) and the 2-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide series compound (V) EC to DL-11 (picking up from Dalian), HLD-15 (picking up from Liaoning Huludao City) 2 kinds of ash arrhizus bacteria Botrytiscinerea50In Table 11. Test result indicate that, through the Compound II per I compound IV that obtains of reduction, ash arrhizus bacteria also had very high bactericidal activity, in the middle of the bactericidal activity test to DL-11 bacterial strain, IV-5 is to the relative virus force multiple of procymidone and of pyrimethanil respectively 4.2 and 11.1, equally to the relative virus force multiple of procymidone and of pyrimethanil respectively 8.0 and 12.6 in the test of HLD-15 bacterial strain. With different acyl chlorides and compound (IV), the compound (V) being bonded into also there is very high bactericidal activity, it is common to higher than comparison medicament procymidone and of pyrimethanil. In the middle of the test of DL-11 bacterial strain, the relative virus force multiple best result of procymidone and of pyrimethanil is not reached 163.3 and 431.0, in the test of HLD-15 bacterial strain, the relative virus force multiple best result of procymidone Yu of pyrimethanil is not reached 3.2 and 5.0.
The table 10 Compound II per I EC to 2 kinds of ash arrhizus bacterias50Value
Table 11 compound IV and the V EC to 2 kinds of ash arrhizus bacterias50Value
The example 6. compound (III, IV, V) bactericidal activity to other plant pathogenic fungi
With reference to farm-chemical indoor determination test rule, adopt Plating (suppressing mycelial growth experiment), by the pastille culture medium that concentration is 50 �� g/mL, determine 2-oxo-2-substituted-phenyl ethyl sulfonamide compounds (III) bactericidal activity to the big speckle of Semen Maydis, Fructus Cucumidis sativi reaping hook, Phytophthora capsici, cereal reaping hook, Cucumber Target Leaf Spot and rice banded sclerotial blight pathogenic fungi, with Bravo for comparison medicament. Target compound 2-hydroxyl-2-substituted-phenyl b-sulfonamide compound (IV) is mould to melon and fruit corruption, the bactericidal activity of rice banded sclerotial blight, cereal reaping hook pathogenic fungi, with carbendazim for comparison medicament. 2-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide compounds (V) to Oryza sativa L. rice blast, soybean root rot, cereal reaping hook, rice banded sclerotial blight, the big speckle of Semen Maydis, Phytophthora capsici, Fructus Cucumidis sativi brown patch, the rotten mould pathogenic fungi of melon and fruit bactericidal activity, with procymidone and of pyrimethanil for comparison medicament, arranging acetone solvent is blank, and each process is in triplicate. After the bacterium colony in blank fully grows, measure the colony diameter of each process with decussation method, take its meansigma methods, calculate suppression ratio by below equation:
Suppression ratio (%)=(blank colony diameter-pastille medium colony diameter)/(blank colony diameter-bacterium cake diameter) �� 100%
Result shows that 6 kinds of pathogenic fungi are all had bactericidal activity (table 12) by Compound II per I, and the highest suppression ratio to Exserohilum turcicum is 64.0%; The suppression ratio of Fructus Cucumidis sativi reaping hook pathogenic bacteria is higher than control compound B-1 by 6 compounds, and the highest suppression ratio has reached 72.2%; The activity of P. capsici is general higher, and the suppression ratio of most compounds is higher than 80%, and the highest suppression ratio is 91.0%, and wherein the activity of 6 compounds is higher than comparison medicament B-1 and Bravo; The activity of cereal reaping hook pathogenic bacteria is also general higher, and the suppression ratio of most compounds is higher than 70%, and the highest suppression ratio is 91.7%, and wherein the activity of 12 compounds is higher than comparison medicament B-1 and Bravo; Having 11 compounds activity to cucumber aphid higher than comparison medicament B-1 and Bravo, the highest suppression ratio reaches 68.0%;Having 12 compounds activity to Rhizoctonia solani Kuhn higher than comparison medicament B-1 and Bravo, the highest suppression ratio reaches 75.7%.
Compound IV is mould to melon and fruit corruption, rice banded sclerotial blight, cereal reaping hook pathogen have significantly high bactericidal activity (table 13), and the highest suppression ratio to 3 kinds of pathogen is 83.4%, 100%, 100% respectively, and compares medicament carbendazim activity quite.
The control spectrum determination of table 122-oxo-2-substituted-phenyl ethyl sulfonamide compounds III
The control spectrum determination of table 132-hydroxyl-2-substituted-phenyl ethyl sulfonamide compounds (IV)
8 kinds of pathogenic fungi of test are respectively provided with good bactericidal activity (table 14) by 2-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide series compound V. The suppression ratio of rice blast fungus is higher than 90% by 4 compounds, and the suppression ratio of 2 compounds has reached 100%; The suppression ratio of pathogen of soybean root rot is higher than 70% by 2 compounds, and the highest suppression ratio reaches 79.2%; The suppression ratio of cereal reaping hook pathogenic bacteria is higher than 70% by 4 compounds, and the highest suppression ratio has reached 79.5%; The suppression ratio of Rhizoctonia solani Kuhn is higher than 70% by 4 compounds, and the highest suppression ratio reaches 93.8%; The suppression ratio of P. capsici is higher than 70% by 4 compounds, and the highest suppression ratio reaches 89.5%; The suppression ratio of Pythium aphanidermatum is higher than 70% by 2 compounds, and the highest suppression ratio reaches 72.9%.
The control spectrum determination of table 14 compound 2-acyloxy-2-(3,5-difluorophenyl) ethyl sulfonamide series compound V
The Concentraton gradient of various plants pathogenic fungi bactericidal activity is measured by example 7. compound (III, IV, V)
With reference to farm-chemical indoor determination test rule, adopt Plating (suppressing mycelial growth experiment), sample compound is made g/mL5 original concentration of 10000,2500,625,156,39 �� with acetone respectively. Under aseptic condition, dilute 100 times of pastille culture medium obtaining 100,25,6.25,1.56,0.39 g/mL5 concentration of �� with PDA (potato dextrose medium). The truffle of inoculation diameter 5mm, cultivates 3-5 days at about 23 DEG C. Measure colony diameter (decussation method). EXCEL software statistics method is utilized to calculate EC50Value, comparative compound III, IV, V poison of drug power size.
Test result indicate that Compound II per I, IV, V be mould to cereal reaping hook, rice banded sclerotial blight, melon and fruit corruption, Fructus Cucumidis sativi brown patch, Phytophthora capsici all have higher bactericidal activity (table 15). The activity of 5 kinds of pathogen is generally higher than comparison medicament B-1 by Compound II per I, respectively reach 5.2,3.9,2.3,1.1,1.4 with the highest relative virus force multiple of the B-1 above pathogen of phase comparison, do not reached 5.5 and 7.7 with the relative virus force multiple best result of Bravo phase comparison Fructus Cucumidis sativi brown patch and P. capsici. Compound IV-5 and B-1 phase comparison cereal reaping hook, rice banded sclerotial blight, melon and fruit corruption relative virus force multiple mould, Fructus Cucumidis sativi brown patch are 1.3,1.2,2.6,1.0 respectively, are 5.5 and 6.2 respectively with the relative virus force multiple of Bravo phase comparison Fructus Cucumidis sativi brown patch and P. capsici. The highest relative virus force multiple of the above-mentioned 5 kinds of pathogenic fungi of compound V and B-1 phase comparison is 1.7,2.2,2.4,2.6,1.0 respectively, is 17.1 and 5.3 respectively with the relative virus force multiple of Bravo phase comparison Fructus Cucumidis sativi brown patch and P. capsici.
The table 15 compound (III, IV, V) EC to plant pathogenic fungi50Value
Claims (3)
1.2-oxo, 2-hydroxyl and 2-acyloxy-2-substituted-phenyl b-sulfonamide compound, is characterized in that: the series compound III shown in following formula, IV and V
III-1��III-20:III-1:R1=3,4-(F)2;III-2:R1=3-Cl; III-3:R1=4-Cl; III-4:R1=2,4-(Cl)2; III-5:R1=4-Br; III-6:R1=2-CH3; III-7:R1=4-NO2; III-8:R1=3,5-(CF3)2; III-9:R1=4-F-3-CF3,III-10:R1=2,4-(Cl)2-5-F; III-11:R1=4-OCH3; III-12:R1=2-Cl; III-13:R1=2-Cl-3-F; III-14:R1=2-CF3; III-15:R1=3,5-(F)2; III-16:R1=4-CF3; III-17:R1=2-F; III-18:R1=2-NO2; III-19:R1=3-F; III-20:R1=3-CF3;
IV-1��IV-5:IV-1:R1=H; IV-2:R1=3-F; IV-3:R1=4-NO2; IV-4:R1=3,4-(F)2; IV-5:R1=3,5-(F)2��
V-1��V-20:R1=3,5-(F)2;
V-1:R2=C2H5; V-2:R2=CH3; V-3:R2=3-pyridine radicals; V-4:R2=2-furyl; V-5:R2=2-ClC6H4; V-6:R2=3-FC6H4; V-7:R2=2-FC6H4; V-8:R2=CCl3; V-9:R2=CHCl2; V-10:R2=3-CH3C6H4; V-11:R2=2-CH3C6H4; V-12:R2=3-CF3C6H4; V-13:R2=2-CF3C6H4; V-14:R2=3-ClC6H4; V-15:R2=CH3CH2OCH2; V-16:R2=CH3(CH2)2CH2; V-17:R2=ClCH2CH2; V-18:R2=2,4-(CH3)2C6H3; V-19:R2=4-CH3C6H4; V-20:R2=4-OCH3C6H4��
2. the synthetic method of the Compound II per I described in claim 1, IV and V, its synthetic route is:
R in formula1, R2Implication with claim 1;
By substituted acetophenone (I), 1, 2-dichloroethanes, sulfur trioxide dioxane complex, potassium carbonate prepares 2-oxo-2-substituted-phenyl ethyl group sulfonic acid potassium salt (II) under certain condition, and then at room temperature by 2-oxo-2-substituted-phenyl ethyl group sulfonic acid potassium salt, anhydrous methylene chloride, N, dinethylformamide, the reactant liquor of oxalyl chloride is added drop-wise in 2-trifluoromethyl-4-chloroaniline, obtain 2-oxo-2-substituted-phenyl ethyl group sulfonamide (III), Compound II per I is reducing carbonyl when 1% sodium hydroxide+methanol+sodium borohydride, obtain 2-hydroxyl-2-substituted-phenyl ethyl sulfonamide (IV), further from the various different replacement type acyl chlorides being synthetically derived to being bonded into new 2-acyloxy-2-substituted-phenyl ethyl sulfonamide (V) series compound.
3. the compound described in claim 1 is as the purposes of disinfectant use in agriculture, it is characterized in that:, cereal reaping hook, Phytophthora capsici mould for multiple tomato gray mould, rice banded sclerotial blight, Oryza sativa L. rice blast, the big speckle of Semen Maydis, melon and fruit corruption, Fructus Cucumidis sativi brown patch, Fructus Cucumidis sativi reaping hook, the rotten mould pathogen of melon and fruit and agricultural plant disease preventing and treating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610140209.7A CN105646298B (en) | 2016-03-11 | 2016-03-11 | 2 oxos, 2 hydroxyls and 2 acyloxy, 2 substituted-phenyl b-sulfonamide compound and preparation method and the purposes as fungicide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610140209.7A CN105646298B (en) | 2016-03-11 | 2016-03-11 | 2 oxos, 2 hydroxyls and 2 acyloxy, 2 substituted-phenyl b-sulfonamide compound and preparation method and the purposes as fungicide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105646298A true CN105646298A (en) | 2016-06-08 |
| CN105646298B CN105646298B (en) | 2018-04-13 |
Family
ID=56493529
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610140209.7A Expired - Fee Related CN105646298B (en) | 2016-03-11 | 2016-03-11 | 2 oxos, 2 hydroxyls and 2 acyloxy, 2 substituted-phenyl b-sulfonamide compound and preparation method and the purposes as fungicide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105646298B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316897A (en) * | 2016-07-28 | 2017-01-11 | 沈阳农业大学 | 2-substituted aminocycloalkylsulfonamide compound, preparation method and application thereof |
| CN107337620A (en) * | 2017-05-23 | 2017-11-10 | 沈阳农业大学 | 2 amide groups b-sulfonamide compounds, preparation method and the purposes as bactericide, herbicide |
| CN109810029A (en) * | 2019-02-27 | 2019-05-28 | 沈阳农业大学 | 2- replaces ethylamine basic ring alkyl sulfonyl amine compounds and its preparation method and application |
| CN113402426A (en) * | 2021-07-29 | 2021-09-17 | 沈阳农业大学 | N-substituted-3, 3-dimethyl-2-oxobutanesulfonamide compound and preparation method and application thereof |
| CN113563238A (en) * | 2021-07-29 | 2021-10-29 | 沈阳农业大学 | 2-phenoxyethylamino cyclohexane sulfonamide compound and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058897A (en) * | 2012-12-27 | 2013-04-24 | 苏州大学 | Method for preparing chiral beta-hydroxy sulfonamide |
-
2016
- 2016-03-11 CN CN201610140209.7A patent/CN105646298B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058897A (en) * | 2012-12-27 | 2013-04-24 | 苏州大学 | Method for preparing chiral beta-hydroxy sulfonamide |
Non-Patent Citations (3)
| Title |
|---|
| 李兴海 等: "2-氧代-2-苯基乙磺酰胺化合物组合合成与杀菌活性研究", 《农药学学报》 * |
| 李兴海 等: "2-氧代和2-羟基环烷基磺酰胺对14种病原真菌的杀菌活性", 《农药学学报》 * |
| 李兴海 等: "苯甲酰基甲磺酰胺的合成与杀菌活性", 《农药学学报》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316897A (en) * | 2016-07-28 | 2017-01-11 | 沈阳农业大学 | 2-substituted aminocycloalkylsulfonamide compound, preparation method and application thereof |
| CN106316897B (en) * | 2016-07-28 | 2018-06-22 | 沈阳农业大学 | 2- substituted-amino naphthene sulfamide amine compounds and its preparation method and application |
| CN107337620A (en) * | 2017-05-23 | 2017-11-10 | 沈阳农业大学 | 2 amide groups b-sulfonamide compounds, preparation method and the purposes as bactericide, herbicide |
| CN107337620B (en) * | 2017-05-23 | 2019-07-26 | 沈阳农业大学 | 2- amide groups b-sulfonamide compound, preparation method and the purposes as fungicide, herbicide |
| CN109810029A (en) * | 2019-02-27 | 2019-05-28 | 沈阳农业大学 | 2- replaces ethylamine basic ring alkyl sulfonyl amine compounds and its preparation method and application |
| CN113402426A (en) * | 2021-07-29 | 2021-09-17 | 沈阳农业大学 | N-substituted-3, 3-dimethyl-2-oxobutanesulfonamide compound and preparation method and application thereof |
| CN113563238A (en) * | 2021-07-29 | 2021-10-29 | 沈阳农业大学 | 2-phenoxyethylamino cyclohexane sulfonamide compound and preparation method and application thereof |
| CN113402426B (en) * | 2021-07-29 | 2023-05-26 | 沈阳农业大学 | N-substituted-3, 3-dimethyl-2-oxo-butanesulfonamide compound as well as preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105646298B (en) | 2018-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105646298A (en) | 2-oxo-, 2-hydroxyl and 2-acyloxy-2-substituted phenyl ethyl sulfonamide compound and preparation method and application thereof as bactericide | |
| CN106916084B (en) | A kind of malononitrile oximido ether compound and application thereof | |
| Lu et al. | Synthesis and evaluation of anti-tubercular and antibacterial activities of new 4-(2, 6-dichlorobenzyloxy) phenyl thiazole, oxazole and imidazole derivatives. Part 2 | |
| KR100796851B1 (en) | 1-4-sulfamylaryl-3-substituted-5-aryl-2-pyrazolines as inhibitors of cyclooxygenase-2 | |
| US11033029B2 (en) | Pyrazole amide compound and use thereof | |
| PT775696E (en) | AMINOACID AMID DERIVATIVES PROCESS FOR ITS FUNGICIDE PRODUCTION FOR AGRICULTURAL AND HORTICULTURAL USE AND PROCESS FOR FUNGICIDAL TREATMENT | |
| CN105669541B (en) | 2- amide groups naphthene sulfamide amine compounds and preparation method and as sterilization, herbicide purposes | |
| CN108997253B (en) | Mandelic acid derivatives containing 1,3, 4-oxadiazole thioether and application thereof | |
| CA2478232C (en) | Heterocyclic amide derivatives as cytokine inhibitors | |
| PT1590321E (en) | Aryl alkyl carbamate derivatives production and use thereof in therapy | |
| CN106432125A (en) | 2,5-substituent-1,3,4-oxadiazole (thiadiazole) thioether derivatives as well as preparation method and application thereof | |
| KR900001196B1 (en) | Process for preparing pyrazol derivatives | |
| CN107674070B (en) | Cyanoimine thiazolidine furan carboxamide compound and preparation method and application thereof | |
| CN110294749B (en) | (S) -1, 3-thiazole phenyl furan thiocarbamate compound and preparation method and application thereof | |
| Su et al. | Synthesis and biological evaluation of novel sulfone derivatives containing 1, 3, 4-oxadiazole moiety | |
| US20080108676A1 (en) | Benzothiazolecarboxamides | |
| CN108440412B (en) | 2-pyrazole amide cyclohexyl sulfonamide compound, preparation method and application thereof | |
| CN112209894B (en) | 5-aryl substituted 2-aminobenzoxazole derivative, preparation method and application thereof | |
| RU2676329C2 (en) | Tert-butyl-n-[2-{4-[6-amino-5-(2,4-difluorobenzoyl)-2-oxopyridin-1(2h)-yl]-3,5-difluorophenyl}ethyl]-l-alaninate or salt, hydrate or solvate thereof | |
| Ning et al. | Synthesis, bioactivity and 3D-QSAR of azamacrolide compounds with a carbamate or urea moiety as potential fungicides and inhibitors of quorum sensing | |
| CN106431977B (en) | A kind of unsaturated oximido ethers compound and application thereof | |
| CN105541753B (en) | A kind of carboxamide derivative containing thiazole ring and its preparation and application | |
| CN111454186B (en) | Aryl formanilide compound containing pentafluorothio and preparation method and application thereof | |
| RU2809004C1 (en) | Use of 1-acetyl-2-[2-(4-chlorophenyl)-2-oxoethyl]indolin-3-one as antifungal agent against yeast fungi | |
| CN116874441A (en) | Flexible aryl formamide derivative containing 1,2, 4-oxadiazole as well as preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180413 Termination date: 20210311 |