CN104211621A - Naphthenic sulfonamide compound, preparation method and application thereof - Google Patents
Naphthenic sulfonamide compound, preparation method and application thereof Download PDFInfo
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- CN104211621A CN104211621A CN201410386378.XA CN201410386378A CN104211621A CN 104211621 A CN104211621 A CN 104211621A CN 201410386378 A CN201410386378 A CN 201410386378A CN 104211621 A CN104211621 A CN 104211621A
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- aminated compounds
- naphthene sulfamide
- sterilant
- preparation
- caul2013
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- MNGVCKIFESJOFC-UHFFFAOYSA-N [NH-]C1(CC1)C(CN=O)O Chemical compound [NH-]C1(CC1)C(CN=O)O MNGVCKIFESJOFC-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of agricultural chemistry and especially relates to a naphthenic sulfonamide compound, a preparation method and an application thereof. The preparation method includes following steps: (1) with 1-chlorocyclopropylethanone as a raw material, carrying out sulphonation to an [alpha]position of a carbonyl with a composite composed of sulfur trioxide and dioxane, and performing neutralization with an alkali to obtain a sulphonate; (2) carrying out a reaction between the sulphonate and oxalyl chloride to form sulfonyl chloride under a catalytic condition by DMF; and (3) finally carrying out a reaction between the oxalyl chloride with amine to obtain 1-chlorocyclopropylcarbonylmethanesulfonamide (CAUL2013-H). The CAUL2013-H compound in the invention can be dissolved in a solvent. With addition of a surfactant, such as pesticide emulsifier 0203B, pesticide emulsifier 0208, GFC, OP-10, tween-60 and the like, and a penetrating agent, such as a penetrating agent JFC, OE-35 and the like, the naphthenic sulfonamide compound can be prepared into an emulsifiable concentrate or a wettable powder with the surfactant and the penetrating agent in a certain proportion. The CAUL2013-H compound has excellent growth-inhibiting effects on sclerotinia sclerotiorum, botrytis cinerea, magaporthe grisea, phomopsis asparagi, rhizoctonia solani and phytophythora capsici.
Description
Technical field
The invention belongs to agrochemistry technical field, particularly a kind of naphthene sulfamide aminated compounds and preparation method thereof and application.
Background technology
Naphthene sulfamide aminated compounds has good fungicidal activity mostly, and part has value (kingly way congruence, the ZL200510085408.4 of exploitation further; Liang Xiaomei etc., ZL200910078883.7).The 1-chlorine cyclopropyl carbonyl Toluidrin that the present invention relates to is novel structure, the diverse compound of type.
Summary of the invention
Not enough for prior art, the invention provides a kind of naphthene sulfamide aminated compounds and preparation method thereof and application.
A kind of naphthene sulfamide aminated compounds, the general structure of described naphthene sulfamide aminated compounds (CAUL2013-H) is as follows:
Wherein, R is C
6h
5-, 3-NO
2-C
6h
4-, 4-CF
3o-C
6h
4-, C
10h
7-, 4-CH
3-C
6h
4-, 4-Br-C
6h
4-, 3-Cl-C
6h
4-, 3,5-(CF
3)
2-C
6h
3-, 2-CF
3-4-Cl-C
6h
3-, 4-Cl-C
6h
4-, C
6h
5cH
2-, 4-CF
3-C
6h
4-, 3-NO
2-4-F-C
6h
3-, 3-CF
3-4-NO
2-C
6h
3-or 2,5-(CF
3)
2-C
6h
3-.
A preparation method for naphthene sulfamide aminated compounds, synthetic route is as follows:
Comprise the steps:
With 1-chlorine cyclopropyl ethyl ketone for raw material, carry out sulfonation with the α position of sulphur trioxide dioxane mixture to carbonyl, through in alkali and after obtain sulfonate; React with oxalyl chloride under DMF catalytic condition and form SULPHURYL CHLORIDE, last and substituted aniline is obtained by reacting a kind of naphthene sulfamide aminated compounds, i.e. 1-chlorine cyclopropyl carbonyl Toluidrin (CAUL2013-H).
An application method for naphthene sulfamide aminated compounds, described naphthene sulfamide aminated compounds is for the preparation of sterilant.
One or more for killing in Sclerotinia sclerotiorum, botrytis cinerea pers, cotton rhizoctonia solani, Pyricularia oryzae, asparagus stem wilt bacteria and P. capsici of described sterilant.
A kind of sterilant, the activeconstituents of described sterilant is above-mentioned naphthene sulfamide aminated compounds.
A kind of sterilant missible oil, described sterilant breast oil composition and each constituent mass percentage composition as follows: the above-mentioned naphthene sulfamide aminated compounds of 1% ~ 10%, the emulsifying agent of 5% ~ 15%, the permeate agent of 0.1% ~ 1% and the solvent of surplus; Each constituent mass percentage composition adds up to 100%.
Described emulsifying agent is tensio-active agent, as agriculture breast 0203B, and 0208, GFC, OP-10, Tween-60 etc.Described permeate agent as penetrating agent JFC, permeate agent OE-35 etc.Described solvent can be toluene, dimethylbenzene etc.
A kind of sterilant wettable powder, composition and each constituent mass percentage composition of described sterilant wettable powder are as follows: the above-mentioned naphthene sulfamide aminated compounds of 15% ~ 50%, the tensio-active agent (as tensio-active agent NNO) of 10% ~ 20%, the White Carbon black of 30% ~ 75%; Each constituent mass percentage composition adds up to 100%.
Beneficial effect of the present invention is:
Gained CAUL2013-H compound of the present invention has good Developing restraint effect to Sclerotinia sclerotiorum, botrytis cinerea pers, Pyricularia oryzae, asparagus stem wilt bacteria, cotton rhizoctonia solani, P. capsici; can be used for plant, particularly the chemoproection of farm crop.
Embodiment
The invention provides a kind of naphthene sulfamide aminated compounds and preparation method thereof and application, below in conjunction with embodiment, the present invention will be further described.
Experimental technique described in following each embodiment, if no special instructions, is ordinary 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 methylsulfonic acid sylvite:
5g (0.042mol) 1-chlorine cyclopropyl ethyl ketone and 20mL anhydrous methylene chloride solution are added in 50mL there-necked flask, be placed in the cooling tank of-40 DEG C, add sulphur trioxide dioxane (1:1) mixture 7.0g (0.042mol) under nitrogen protection in batches, control temperature of reaction at-40 DEG C, within about 20 minutes, add, reaction solution becomes scarlet from faint yellow, then gradient increased temperature rises 10 DEG C every 6h, finally at-8 DEG C, react 2h, then take out there-necked flask and add 20mL water in reaction solution, divide water-yielding stratum, dichloromethane layer water extracts 3 times, each consumption is 20mL, combining water layer, pH=7 ~ 8 are neutralized with KOH under frozen water cooling, the aqueous solution becomes yellow, at 60 DEG C of temperature, precipitation falls most of water, obtain clear yellow viscous liquid, yellow solid is had to separate out after cooling, filter to obtain yellow solid product 5.46g, methyl alcohol heat filtering obtains the methanol solution of 1-(1-chlorine cyclopropyl) carbonyl methylsulfonic acid sylvite, solid will be obtained after vacuum rotary steam, white flaky solid 5.04g is obtained after recrystallization, yield is 51%, m.p 112 DEG C ~ 114 DEG C.
1H-NMR(D
2O)：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 Toluidrin:
In 50mL there-necked flask, add 1.0g (0.0042mol) 1-(1-chlorine cyclopropyl) carbonyl methylsulfonic acid sylvite, 20mL anhydrous methylene chloride, DMF mono-, under nitrogen protection, stirring at room temperature 10min.Add and heavily steam oxalyl chloride 0.376mL (0.0042mol), ice-water bath controls reactor temperature at 5 DEG C ~ 15 DEG C, and reaction 60min, to substantially not producing bubble.Frozen water is cooled to 0 DEG C, and suction filtration falls solid, and gained solution moves in dropping funnel.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; the solution of step reaction gained in dropping, control temperature is at 5 DEG C ~ 10 DEG C.Add the rear room temperature that is naturally raised to continue to stir 2h, sample after thin plate chromatography (TLC) determines that raw material primitive reaction completely, stopped reaction.In gained solution, add 10mL methylene dichloride, stir 10min, add 10mL water subsequently and fully stir, separate dichloromethane layer with separating funnel, then wash 2 times with the HCl that concentration is 6mol/L, each consumption is 5mL, wash 2 times again with water, each consumption is after 5mL, uses anhydrous Na
2sO
4dried overnight.Suction filtration falls sodium sulfate, obtains red thick liquid, the sterling pale yellowish oil liquid of column chromatography after precipitation.
Other CAUL2013-H series compounds can be prepared by the same way.The physical constant etc. of part CAUL2013-H series compound is 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-H 1 ~ 10g in 100mL volumetric flask, emulsifying agent 5g ~ 15g, permeate agent 0.1g ~ 1g, then using solvent (as toluene, dimethylbenzene etc.) constant volume to obtain CAUL2013-H massfraction is the missible oil of 1% ~ 10%.
(2) wettable powder: get Compound C AUL2013-H 15g ~ 20g, tensio-active agent 10g ~ 20g, White Carbon black 30g ~ 75g, through mixing and pulverizing CAUL2013-H massfraction is the wettable powder of 15% ~ 50%.
Embodiment 4
The mensuration of CAUL2013-H series compound fungicidal activity:
Measuring method: adopt Activities, the liquid by different concns mixes with thawing substratum, makes the malicious substratum plane of band, inoculates pathogenic bacteria in the plane, judge medicament virulence size with the speed of growth of pathogenic bacteria speed.The fungicidal activity of part 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 data sheet
Show 3CAUL2013-H series compound under 50mg/L concentration to growth inhibition ratio (%) data sheet of six kind of plant pathogenic bacterias
Claims (7)
1. a naphthene sulfamide aminated compounds, is characterized in that, the general structure of described naphthene sulfamide aminated compounds is as follows:
Wherein, R is C
6h
5-, 3-NO
2-C
6h
4-, 4-CF
3o-C
6h
4-, C
10h
7-, 4-CH
3-C
6h
4-, 4-Br-C
6h
4-, 3-Cl-C
6h
4-, 3,5-(CF
3)
2-C
6h
3-, 2-CF
3-4-Cl-C
6h
3-, 4-Cl-C
6h
4-, C
6h
5cH
2-, 4-CF
3-C
6h
4-, 3-NO
2-4-F-C
6h
3-, 3-CF
3-4-NO
2-C
6h
3-or 2,5-(CF
3)
2-C
6h
3-.
2. the preparation method of a kind of naphthene sulfamide aminated compounds as claimed in claim 1, is characterized in that, comprise the steps:
With 1-chlorine cyclopropyl ethyl ketone for raw material, carry out sulfonation with the α position of sulphur trioxide dioxane mixture to carbonyl, through in alkali and after obtain sulfonate; React with oxalyl chloride under catalytic condition and form SULPHURYL CHLORIDE, last and substituted aniline is obtained by reacting a kind of naphthene sulfamide aminated compounds, i.e. 1-chlorine cyclopropyl carbonyl Toluidrin.
3. the application method of a kind of naphthene sulfamide aminated compounds as claimed in claim 1, is characterized in that: described naphthene sulfamide aminated compounds is for the preparation of sterilant.
4. the application method of a kind of naphthene sulfamide aminated compounds according to claim 3, is characterized in that: one or more for killing in Sclerotinia sclerotiorum, botrytis cinerea pers, cotton rhizoctonia solani, Pyricularia oryzae, asparagus stem wilt bacteria and P. capsici of described sterilant.
5. a sterilant, is characterized in that: the activeconstituents of described sterilant is naphthene sulfamide aminated compounds according to claim 1.
6. a sterilant missible oil, it is characterized in that, the breast oil composition of described sterilant and each constituent mass percentage composition as follows: the naphthene sulfamide aminated compounds according to claim 1 of 1% ~ 10%, the emulsifying agent of 5% ~ 15%, the permeate agent of 0.1% ~ 1% and the solvent of surplus; Each constituent mass percentage composition adds up to 100%.
7. a sterilant wettable powder, it is characterized in that, composition and each constituent mass percentage composition of described sterilant wettable powder are as follows: the naphthene sulfamide aminated compounds according to claim 1 of 15% ~ 50%, the tensio-active agent of 10% ~ 20%, the White Carbon black of 30% ~ 75%; Each constituent mass percentage composition adds up to 100%.
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|---|---|---|---|
| CN201410386378.XA CN104211621B (en) | 2014-08-07 | 2014-08-07 | A kind of naphthene sulfamide aminated compounds and preparation method thereof and application |
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| CN104211621B CN104211621B (en) | 2016-05-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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| US4847273A (en) * | 1985-06-21 | 1989-07-11 | Hoffmann-La Roche Inc. | Dihydropyridine derivatives |
| US20060058315A1 (en) * | 2002-11-07 | 2006-03-16 | Astrazeneca Ab | 2-Oxo-ethanesulfonamide derivates |
| 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 |
-
2014
- 2014-08-07 CN CN201410386378.XA patent/CN104211621B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4847273A (en) * | 1985-06-21 | 1989-07-11 | Hoffmann-La Roche Inc. | Dihydropyridine derivatives |
| US20060058315A1 (en) * | 2002-11-07 | 2006-03-16 | Astrazeneca Ab | 2-Oxo-ethanesulfonamide derivates |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| TORNUS INGO ET AL: "Novel applications of N-sulfonyl-alkylamines in [2+4] cycloadditions", 《TETRAHEDRON》 * |
| 汪晓平等: "N-取代-2-氧代环十二烷基磺酰胺的合成及杀菌活性", 《高等学校化学学报》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| CN104211621B (en) | 2016-05-25 |
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Granted publication date: 20160525 Termination date: 20170807 |