CN104211621B - A kind of naphthene sulfamide aminated compounds and preparation method thereof and application - Google Patents
A kind of naphthene sulfamide aminated compounds and preparation method thereof and application Download PDFInfo
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- CN104211621B CN104211621B CN201410386378.XA CN201410386378A CN104211621B CN 104211621 B CN104211621 B CN 104211621B CN 201410386378 A CN201410386378 A CN 201410386378A CN 104211621 B CN104211621 B CN 104211621B
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- naphthene sulfamide
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Abstract
The invention belongs to agriculture chemistry technical field, particularly a kind of naphthene sulfamide aminated compounds and preparation method thereof and application. The present invention is taking 1-chlorine cyclopropyl ethyl ketone as raw material, sulfonation carried out in the α position of carbonyl with sulfur trioxide dioxane compound, through in alkali and after obtain sulfonate. Under DMF catalytic condition, react with oxalyl chloride and form sulfonic acid chloride, finally react with amine and obtain 1-chlorine cyclopropyl carbonyl Methanesulfomide (CAUL2013-H). Gained CAUL2013-H compound of the present invention dissolves in solvent, adds surfactant, as agriculture breast 0203B, and 0208, GFC, OP-10, Tween-60 etc., bleeding agent is as penetrating agent JFC, and OE-35 etc., are hybridly prepared into missible oil or wettable powder by a certain percentage. Gained CAUL2013-H compound of the present invention has good inhibition growth to Sclerotinia sclerotiorum, botrytis cinerea pers, Pyricularia oryzae, asparagus stem wilt bacteria, cotton rhizoctonia solani, Phytophthora capsici germ.
Description
Technical field
The invention belongs to agriculture chemistry technical field, particularly a kind of naphthene sulfamide aminated compounds and preparation side thereofMethod and application.
Background technology
Naphthene sulfamide aminated compounds has good bactericidal activity mostly, and part has the value (king of further exploitationRoad congruence, ZL200510085408.4; Liang Xiaomei etc., ZL200910078883.7). The 1-chlorine cyclopropyl carbonyl the present invention relates toMethanesulfomide is novel structure, the diverse compound of type.
Summary of the invention
For prior art deficiency, the invention provides a kind of naphthene sulfamide aminated compounds and preparation method thereof and answerWith.
A kind of naphthene sulfamide aminated compounds, the structure of described naphthene sulfamide aminated compounds (CAUL2013-H) is logicalFormula is as follows:
Wherein, R is C6H5-、3-NO2-C6H4-、4-CF3O-C6H4-、C10H7-、4-CH3-C6H4-、4-Br-C6H4-、3-Cl-C6H4-、3,5-(CF3)2-C6H3-、2-CF3-4-Cl-C6H3-、4-Cl-C6H4-、C6H5CH2-、4-CF3-C6H4-、3-NO2-4-F-C6H3-、3-CF3-4-NO2-C6H3-or 2,5-(CF3)2-C6H3-。
A preparation method for naphthene sulfamide aminated compounds, synthetic route is as follows:
Comprise the steps:
Taking 1-chlorine cyclopropyl ethyl ketone as raw material, sulfonation is carried out in the α position of carbonyl with sulfur trioxide dioxane compound,Through in alkali and after obtain sulfonate; Under DMF catalytic condition, react with oxalyl chloride and form sulfonic acid chloride, finally react with substituted anilineObtain a kind of naphthene sulfamide aminated compounds, i.e. 1-chlorine cyclopropyl carbonyl Methanesulfomide (CAUL2013-H).
An application process for naphthene sulfamide aminated compounds, described naphthene sulfamide aminated compounds is for the preparation of killingMicrobial inoculum.
Described bactericide is used for killing Sclerotinia sclerotiorum, botrytis cinerea pers, cotton rhizoctonia solani, Pyricularia oryzae, reedOne or more in bamboo shoot stem wilt bacterium and Phytophthora capsici germ.
A kind of bactericide, the active component of described bactericide is above-mentioned naphthene sulfamide aminated compounds.
A kind of bactericide missible oil, described bactericide breast oil composition and each constituent mass percentage composition are as follows: 1%～10%Above-mentioned naphthene sulfamide aminated compounds, 5%～15% emulsifying agent, 0.1%～1% bleeding agent and the solvent of surplus;Each constituent mass percentage composition adds up to 100%.
Described emulsifying agent is surfactant, as agriculture breast 0203B, 0208, GFC, OP-10, Tween-60 etc. Described infiltrationAgent is as penetrating agent JFC, bleeding agent OE-35 etc. Described solvent can be toluene, dimethylbenzene etc.
A kind of bactericide wettable powder, the composition of described bactericide wettable powder and each constituent mass percentage composition asUnder: 15%～50% above-mentioned naphthene sulfamide aminated compounds, 10%～20% surfactant is (as surfactantNNO), 30%～75% White Carbon black; Each constituent mass percentage composition adds up to 100%.
Beneficial effect of the present invention is:
Gained CAUL2013-H compound of the present invention is to Sclerotinia sclerotiorum, botrytis cinerea pers, Pyricularia oryzae, asparagus stemRot bacterium, cotton rhizoctonia solani, Phytophthora capsici germ have good inhibition growth, can be used for plant, particularly farmingThe chemoproection of thing.
Detailed description of the invention
The invention provides a kind of naphthene sulfamide aminated compounds and preparation method thereof and application, below in conjunction with concrete realityThe present invention will be further described to execute mode.
Experimental technique described in following each embodiment, if no special instructions, is conventional method; Described reagent and material,If no special instructions, all can obtain from commercial channels.
Embodiment 1
The preparation of 1-(1-chlorine cyclopropyl) carbonyl methanesulfonic acid sylvite:
5g (0.042mol) 1-chlorine cyclopropyl ethyl ketone and 20mL anhydrous methylene chloride solution are added in 50mL there-necked flask, putPut in the cooling bath of-40 DEG C, under nitrogen protection, add sulfur trioxide dioxane (1:1) compound 7.0g in batches(0.042mol), control reaction temperature at-40 DEG C, within about 20 minutes, add, reactant liquor is from the faint yellow peony that becomes, then terracedDegree heats up and rises 10 DEG C every 6h, finally at-8 DEG C, reacts 2h, and then take out there-necked flask and add 20mL water in reactant liquor, pointWater-yielding stratum, dichloromethane layer water extraction 3 times, each consumption is 20mL, combining water layer, frozen water is cooling neutralizes pH with KOH down=7～8, the aqueous solution becomes yellow, and at 60 DEG C of temperature, precipitation falls most of water, obtains yellow viscous fluid, has after cooling yellow solidBody is separated out, and filters to obtain yellow solid product 5.46g, and methyl alcohol heat filtering obtains the methyl alcohol of 1-(1-chlorine cyclopropyl) carbonyl methanesulfonic acid sylviteSolution, will obtain solid after vacuum rotary steam, obtain white plates solid 5.04g after recrystallization, and yield is 51%, m.p112 DEG C～114℃。
1H-NMR(D2O): 1.52-1.56 (m, 2H), 1.74-1.79 (m, 2H), 4.28 (s, 2H). Embodiment 2
The preparation of 1-chlorine cyclopropyl carbonyl Methanesulfomide:
In 50mL there-necked flask, add 1.0g (0.0042mol) 1-(1-chlorine cyclopropyl) carbonyl methanesulfonic acid sylvite, 20mL withoutWater carrene, mono-of DMF, under nitrogen protection, stirring at room temperature 10min. Add and heavily steam oxalyl chloride 0.376mL (0.0042mol),Ice-water bath control reactor temperature is at 5 DEG C～15 DEG C, and reaction 60min, to substantially not producing bubble. Frozen water is cooled to 0 DEG C, takes outFilter solid, gained solution moves in dropping funel. In another 50mL there-necked flask, under nitrogen protection, add 0.3mL(2.4mmol) triethylamine, aniline 0.397g (0.0042mol), 20mL anhydrous methylene chloride, ice bath is cooled to 0～5 DEG C, dripsThe solution of upper step reaction gained, controls temperature at 5 DEG C～10 DEG C. Add the rear room temperature that is naturally raised to and continue to stir 2h, sampling is through thinPlate layer chromatography (TLC) stops reaction after determining that raw material fundamental reaction completely. In gained solution, add 10mL carrene, stir10min, adds 10mL water fully to stir subsequently, separates dichloromethane layer, the HCl that is then 6mol/L by concentration with separatory funnelWash 2 times, each consumption is 5mL, then washes with water 2 times, after each consumption is 5mL, uses anhydrous Na2SO4Dried overnight. Suction filtrationFall sodium sulphate, after precipitation, obtain red thick liquid, the light yellow oily liquid of sterling of column chromatography.
Other CAUL2013-H series compounds can be prepared by the same way. Part CAUL2013-H series compoundPhysical constants etc. are listed in table 1, and nuclear magnetic resonance data is listed in table 2.
Embodiment 3
The compound method of CAUL2013-H series compound preparation:
(1) missible oil: add Compound C AUL2013-H1～10g in 100mL volumetric flask, emulsifying agent 5g～15g, infiltrationAgent 0.1g～1g, then uses solvent (as toluene, dimethylbenzene etc.) constant volume to obtain the breast that CAUL2013-H mass fraction is 1%～10%Oil.
(2) wettable powder: get Compound C AUL2013-H15g～20g, surfactant 10g～20g, White Carbon black30g～75g, through mixing and pulverizing to obtain the CAUL2013-H mass fraction wettable powder that is 15%～50%.
Embodiment 4
The mensuration of CAUL2013-H series compound bactericidal activity:
Assay method: adopt Activities, mix with thawing culture medium by the liquid of variable concentrations, make bandPoison culture medium plane, inoculates pathogen in the plane, judges medicament virulence size with the speed of pathogen growth rate. PartThe bactericidal activity of CAUL2013-H series compound is listed in table 3.
Table 1 general formula is numbering, substituted radical, the physicochemical data table of the series compound of CAUL2013-H
Table 2CAUL2013-H series compound proton nmr spectra tables of data
Table 3CAUL2013-H series compound growth inhibition ratio to six Plants pathogens (%) under 50mg/L concentrationTables of data
Claims (7)
1. a naphthene sulfamide aminated compounds, is characterized in that, the general structure of described naphthene sulfamide aminated compoundsAs follows:
Wherein, R is C6H5-、3-NO2-C6H4-、4-CF3O-C6H4-、C10H7-、4-CH3-C6H4-、4-Br-C6H4-、3-Cl-C6H4-、3,5-(CF3)2-C6H3-、2-CF3-4-Cl-C6H3-、4-Cl-C6H4-、C6H5CH2-、4-CF3-C6H4-、3-NO2-4-F-C6H3-、3-CF3-4-NO2-C6H3-or 2,5-(CF3)2-C6H3-。
2. the preparation method of a kind of naphthene sulfamide aminated compounds as claimed in claim 1, is characterized in that, synthetic routeFor:
Comprise the steps:
Taking 1-chlorine cyclopropyl ethyl ketone as raw material, sulfonation is carried out in the α position of carbonyl with sulfur trioxide dioxane compound, through hydrogenIn potassium oxide and after obtain sulfonate; Under catalytic condition, react with oxalyl chloride and form sulfonic acid chloride, finally react with substituted anilineObtain a kind of naphthene sulfamide aminated compounds, i.e. 1-chlorine cyclopropyl carbonyl Methanesulfomide;
Wherein, R is C6H5-、3-NO2-C6H4-、4-CF3O-C6H4-、C10H7-、4-CH3-C6H4-、4-Br-C6H4-、3-Cl-C6H4-、3,5-(CF3)2-C6H3-、2-CF3-4-Cl-C6H3-、4-Cl-C6H4-、C6H5CH2-、4-CF3-C6H4-、3-NO2-4-F-C6H3-、3-CF3-4-NO2-C6H3-or 2,5-(CF3)2-C6H3-。
3. the application process of a kind of naphthene sulfamide aminated compounds as claimed in claim 1, is characterized in that: described cycloalkanesBase sulfamide compound is for the preparation of bactericide.
4. the application process of a kind of naphthene sulfamide aminated compounds according to claim 3, is characterized in that: described in killMicrobial inoculum is used for killing Sclerotinia sclerotiorum, botrytis cinerea pers, cotton rhizoctonia solani, Pyricularia oryzae, asparagus stem wilt bacteria and pepperyOne or more in green pepper phytophthora root rot bacterium.
5. a bactericide, is characterized in that: the active component of described bactericide is naphthene sulfamide amine claimed in claim 1Compounds.
6. a bactericide missible oil, is characterized in that, described bactericide breast oil composition and each constituent mass percentage composition are as follows:1%～10% naphthene sulfamide aminated compounds claimed in claim 1,5%～15% emulsifying agent, 0.1%～1%The solvent of bleeding agent and surplus; Each constituent mass percentage composition adds up to 100%.
7. a bactericide wettable powder, is characterized in that, the composition of described bactericide wettable powder and each constituent massPercentage composition is as follows: 15%～50% naphthene sulfamide aminated compounds claimed in claim 1,10%～20% surfaceActivating agent, 30%～75% White Carbon black; Each constituent mass percentage composition adds up to 100%.
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| US4847273A (en) * | 1985-06-21 | 1989-07-11 | Hoffmann-La Roche Inc. | Dihydropyridine derivatives |
| CN1900059A (en) * | 2005-07-20 | 2007-01-24 | 中国农业大学 | 2-keto naphthene sulfamide, its preparing method and use as germicide |
| CN101503381A (en) * | 2009-03-05 | 2009-08-12 | 中国农业大学 | 1-oxo tetralin-2-sulfonic acid amide, preparation thereof and use as bactericide |
| CN102276552A (en) * | 2011-06-15 | 2011-12-14 | 中国农业大学 | 1,3,4-thiadiazoline derivative containing cyclopropanyl, preparation method thereof and application thereof as bactericide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2003276458A1 (en) * | 2002-11-07 | 2004-06-07 | Astrazeneca Ab | 2-oxo-ethanesulfonamide derivates |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847273A (en) * | 1985-06-21 | 1989-07-11 | Hoffmann-La Roche Inc. | Dihydropyridine derivatives |
| CN1900059A (en) * | 2005-07-20 | 2007-01-24 | 中国农业大学 | 2-keto naphthene sulfamide, its preparing method and use as germicide |
| CN101503381A (en) * | 2009-03-05 | 2009-08-12 | 中国农业大学 | 1-oxo tetralin-2-sulfonic acid amide, preparation thereof and use as bactericide |
| CN102276552A (en) * | 2011-06-15 | 2011-12-14 | 中国农业大学 | 1,3,4-thiadiazoline derivative containing cyclopropanyl, preparation method thereof and application thereof as bactericide |
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