CN106316897B - 2- substituted-amino naphthene sulfamide amine compounds and its preparation method and application - Google Patents
2- substituted-amino naphthene sulfamide amine compounds and its preparation method and application Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/30—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
- C07C311/36—Sulfonamides, the carbon skeleton of the acid part being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups having the sulfur atom of at least one of the sulfonamide groups bound to a carbon atom of a ring other than a six-membered aromatic ring
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- 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
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- 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
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- 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
- A01N43/74—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- 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
- C07C303/30—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 by reactions not involving the formation of esterified sulfo groups
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- 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
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- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/36—Radicals substituted by singly-bound nitrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings 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
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Abstract
The present invention provides a kind of 2 substituted-amino naphthene sulfamide amine compounds, have the structure as shown in formula (I), wherein：R1Alkyl selected from H or C1 C6；R2One kind in substituted or non-substituted alkyl, substituted or non-substituted phenethyl, substituted or non-substituted phenylpropyl, substituted or non-substituted pyridyl group, substituted or non-substituted thiazolyl, substituted or non-substituted carboxylate, substituted or non-substituted acetamido selected from C1 C8；M is selected from 1,2 or 3.Compound provided by the invention can be used as herbicide or fungicide, have inhibiting effect to the pathogen of the diseases such as tomato gray mould, rice banded sclerotial blight, rice rice blast, the big spot of corn, Root Rot of Wheat, melon withered, capsicum epidemic disease, for the prevention of agricultural plant disease；To Amaranthus retroflexus, piemarker, barnyard grass, lady's-grass etc., common farmland list broadleaf weed has the function of to inhibit growth.
Description
Technical field
The present invention relates to field of agrochemicals, and in particular to one kind contains 2- substituted amido naphthene sulfamide amine chemical combination
The synthesis of object and conduct fungicide and herbicide.
Background technology
Application of the Novel ring alkyl sulfonyl amine compound in disinfectant use in agriculture is originating from the full seminar of kingly way in 1997
(Wang Xiaoping waits Chemical Journal of Chinese Universities, 1997,18 (6) to the 2- oxo cyclo-dodecyls sulfamide compound that year is reported:
889-893), there is preferably suppression to fusarium graminearum Gibberllazeae and pear cucumerinum Venturianashicola
System activity.On subsequent Research foundation, candidate novel fungicides agent-Hexanaphthene flusulfamide A (exploitation code name CAUWL-2004-L-13)
It is developed, available for diseases such as prevention graw mold of tomato, sclerotinia sclerotiorum, Cucumber Target Leaf Spot and scabs.
In order to further obtain the excellent noval chemical compound of bactericidal activity, successively there are 2- hydroxycycloalkyl sulfamide compounds
(Li Xing-hai,et al.JAgr Food Chem,2010,58(21):11384-11389), 2- acyloxy cyclohexyl sulphur
Amides compound (Li Xing-hai, etal.Int J MolSci, 2013,14 (11):22544-22557), 1- oxos four
Hydrogen naphthalene -2- sulfamide compounds, 5- oxyl -2- oxocyclohex alkyl sulfonyl amine compounds, 1- chlorine cyclopropyl carbonyls
Methylsulfonyl aminated compounds is synthesized to obtain, they all have good bactericidal activity.
Invention content
On the basis of the studies above, present invention synthesis obtains a kind of new, has good bactericidal activity and activity of weeding
2- substituted-amino naphthene sulfamide amine compounds, specifically, 2- substituted-aminos naphthene sulfamide amine compounds provided by the invention
Object has the structure as shown in formula (I),
Wherein：R1Alkyl selected from H or C1-C6；R2It is substituted or non-substituted alkyl selected from C1-C8, substituted or non-substituted
Phenethyl, substituted or non-substituted phenylpropyl, substituted or non-substituted pyridyl group, substituted or non-substituted thiazolyl, substitution
Or one kind in non-substituted carboxylate, substituted or non-substituted acetamido；M is selected from 1,2 or 3.
Preferably, the R1Selected from H, 4-CH3-、5-C2H5-、5-n-C3H7-、5-n-C5H11In any one；
The substituent R2Selected from CH2=CHCH2-、CH3(CH2)2-、CH3(CH2)3-、CH3(CH2)4-、C6H5CH2-、4-
CH3C6H4-CH2-、3-CH3C6H4-CH2-、4-BrC6H4-CH2-、3-FC6H4-CH2-、2-CH3C6H4-CH2-、4-FC6H4-CH2-、
2-FC6H4-CH2-、4-CF3OC6H4-CH2-、2-Cl-5-FC6H3-CH2-、2-BrC6H4-CH2-、3-ClC6H4-CH2-、4-
CNC6H4-CH2-、4-NO2C6H4-CH2-、4-FC6H4-(CH2)2-、C6H5(CH2)2-、4-NO2C6H4-(CH2)2-、C6H5(CH2)3-、
CH3CH2COOCH2-、CH3COOCH2-、CH3CH2COOCH(CH3)-、CH3COOCH(CH3)-、2-chloro-
chloromethylpyridine、2-Chloro-5-chloromehtylthiazole、2-CH3C6H4NHCO-CH2-、4-
FC6H4NHCO-CH2-、4-CH3OC6H4NHCO-CH2-、C6H5NHCO-CH2-、3-BrC6H4NHCO-CH2-、3-FC6H4NHCO-
CH2-、3-CH3OC6H4NHCO-CH2-、3-CF3C6H4NHCO-CH2-、2-CF3OC6H4NHCO-CH2-、2-BrC6H4NHCO-CH2-、
2,5-2FC6H3NHCO-CH2-、2,4-2FC6H3NHCO-CH2-、3-F-4-Br-C6H3NHCO-CH2-、2-F-4-Br-C6H3NHCO-
CH2-、3,5-2CF3C6H3NHCO-CH2-、2-CF3-4-F-C6H3NHCO-CH2-、2-F-4-Cl-C6H3NHCO-CH2-、3-CN-4-
F-C6H3NHCO-CH2-、2-CF3C6H4NHCO-CH2-、3,4-2FC6H3NHCO-CH2-、2,4,5-3FC6H2NHCO-CH2-、2,3,
4-3FC6H2NHCO-CH2-、3-CF3C6H4-CH2NHCO-CH2-、2-CH3C6H4-CH2NHCO-CH2-、2-CH3OC6H4-CH2NHCO-
CH2In any one.
It is highly preferred that the one kind of the compound in following structural formula:
The present invention also provides the preparation method of any of the above-described 2- substituted-aminos naphthene sulfamide amine compounds, above-mentioned formulas
(I) synthetic route of compound represented is：
In formula (II)-(V), R1And R2Definition with claim 1；
Specifically synthetic method is：Using the cyclanone shown in formula (V) as raw material, sulfonated reaction generation, chlorination reaction, amine
Change the 2- keto naphthene sulfamide amine compounds shown in reaction production (IV)；
Again using the 2- keto naphthene sulfamides amine compounds shown in formula (IV) as raw material, formula is synthesized through reduction amination
(III) the 2- aminocycloalkyl sulfonamide compounds shown in；
Again using the 2- aminocycloalkyls sulfonamide compounds shown in formula (III) as raw material, tried with the alkylation shown in formula (II)
Agent is reacted, and obtains the 2- substituted-amino naphthene sulfamide amine compounds shown in formula (I).
The present invention also provides the purposes of any of the above-described 2- substituted-aminos naphthene sulfamide amine compounds, are used particularly as agricultural
Fungicide.
Preferably, for kill tomato gray mould, rice banded sclerotial blight, rice rice blast, the big spot of corn, Root Rot of Wheat, it is melon it is withered,
It is one or more in Phytophthora capsici.
The present invention also provides another purposes of any of the above-described 2- substituted-aminos naphthene sulfamide amine compounds, specific to use
Make agriculture herbicide.
Preferably, for the prevention of farmland monocotyledon weed and broadleaf weed.
The present invention also provides a kind of herbicide, main component is any of the above-described 2- substituted-amino naphthene sulfamides
Amine compounds.
The 2- substituted-amino naphthene sulfamide amine compounds of the offer of the present invention are to tomato gray mould, rice banded sclerotial blight, rice rice
The pathogens such as the big spot of pest, corn, Root Rot of Wheat, melon withered, capsicum epidemic disease have inhibiting effect, for the prevention of its disease；It is right
The common farmland list broadleaf weed such as Amaranthus retroflexus, piemarker, barnyard grass, lady's-grass has the function of to inhibit growth.
Specific embodiment
In order to which those skilled in the art is enable to more fully understand, technical scheme of the present invention is practiced, with reference to specific
The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
Experimental method described in following each embodiments is conventional method unless otherwise specified；The reagent and material,
Unless otherwise specified, it can be commercially available on the market.
Embodiment 1
The preparation of compounds Ⅳ -1~IV -8, preparation method particular reference 1-3, specific synthesis route is such as
Under：
Main raw material substitution cyclanone, 2- trifluoromethyl -4- chloroanilines and other drugs and reagent are market sale
Product, wherein compounds Ⅳ -1N- (2- trifluoromethyl-4-chlorophenyls) -2- oxocyclohex alkyl sulfonamide, compounds Ⅳ -
2N- (2- trifluoromethyl-4-chlorophenyls) -2- oxo-cyclopentane bases sulfonamide, compounds Ⅳ -3N- (2- trifluoromethyl -4- chlorobenzenes
Base) -2- oxo cycloheptyls alkyl sulfonamide independently synthesized for laboratory, specific synthetic method reference literature 1 and document 2.
Synthesis for compounds Ⅳ -4~IV -8, above-mentioned substituted cyclanone is respectively CH3-、C2H5-、C3H7-、C5H11-
Wait substituent groups substitution.
Compounds Ⅳ -4 to IV -8 synthetic method is：0.2mol is replaced into cyclanone, 50mL 1,2- dichloroethanes adds in
In 100mL there-necked flasks, ice bath is cooled to -5 DEG C, and molar ratio 1 is added portionwise under nitrogen protection and stirring:1 aoxidizes for 0.2mol tri-
The molar ratio of the compound of sulphur and dioxane, wherein sulfur trioxide and dioxane is 1:1；2h is reacted between -5-5 DEG C
Afterwards, 30mL water is added in into reaction solution, separates water layer, dichloroethanes layer is extracted with water (30mL × 3), and combining water layer uses Ba
(OH)2·8H2In O and H2SO4, there is BaSO4Precipitation generation when reaching titration end-point, filters, and filtrate uses carbon under ice water cooling
Sour potassium is neutralized to pH=7-8, is filtered again, and filtrate obtains clear yellow viscous liquid in 60 DEG C or so reduced pressures, has the yellow brilliant after cooling
Body is precipitated, and filters to obtain yellow solid product, 2- oxocycloalkyl base sulfonate is obtained with recrystallizing methanol, by it in vacuum drying chamber
It is spare after 100 DEG C of dry 5h.
Dried 0.01mol 2- oxocycloalkyl bases sulfonate, 15mL dichloromethane, 0.1mL DMF are added in into 50mL tri-
In mouth bottle, under nitrogen protection, 10min is stirred at room temperature；0.01mol oxalyl chlorides are added in, reactor temperature is at 5-15 DEG C, reaction
1h, until not generating bubble；Ice water is cooled to 0 DEG C, leaches out solid, and acquired solution is moved in dropping funel.
In another 50mL three-necked flasks, add in 0.01mol triethylamines, 0.008mol 2- trifluoromethyl -4- chloroanilines,
10mL dichloromethane is cooled to 0-5 DEG C, the solution of gained is walked in dropwise addition, controls temperature<10℃；It is raised to room temperature naturally after adding
Continue to stir 2h, stop reaction.
20mL dichloromethane is added in into acquired solution, stirs 10min, then adds in after 10mL water is sufficiently stirred and filters,
Dichloromethane layer is separated, is washed with the HCl (5mL × 2) of 6mol/L, after water (5mL × 2) washing, uses anhydrous Na2SO4It is dried
Night；It filters, is concentrated under reduced pressure, the mixed solvent crystallization through acetone and petroleum ether obtains target product.
The yield and physicochemical property of compounds Ⅳ -4~IV -8 is shown in Table 1, and nucleus magnetic hydrogen spectrum is shown in Table 2 with ir data.
Bibliography 1：Kingly way is complete, Li Xinghai, Liang Xiaomei, Yang Xinling, Chen Fu weighing apparatus .2- keto naphthene sulfamide amine, system
Preparation Method and the purposes as fungicide, Chinese invention patent, application number 200510085408.4,2005-7-20.
Bibliography 2：Li Xing-hai,Wu De-cai,Qi Zhi-qiu,Li Xiu-wei,Gu Zu-min,Wei
Song-hong,Zhang Yang,Wang Ying-zi,Ji Ming-shan.Synthesis,Fungicidal Activity,
and Structure-Activity Relationship of 2-Oxo and 2-
Hydroxycycloalkylsulfonamides.Journal ofAgricultural and Food Chemistry,2010,
58(21):11384–11389.
Bibliography 3：Li Xing-hai,Yang Xin-ling,Liang Xiao-mei,Kai Zhen-peng,Yuan
Hui-zu,Yuan De-kai,Zhang Jian-jun,Wang Rui-qing,Ran Fu-xiang,Qi Shu-hua,Ling
Yun,Chen Fu-heng,Wang Dao-quan.Synthesis and biological activities of2-
oxocycloalkylsulfonamides.Bioorganic&Medicinal Chemistry,2008,16(8):4538-
4544.
The physicochemical property and yield of 1 compounds Ⅳ -4~IV -8 of table
The nuclear magnetic resonance spectroscopy and infrared spectrum of 2 compounds Ⅳ -4~IV -8 of table
Embodiment 2
The preparation of compound III -1~III -8
With reference to the method prepare compound III -1~III -8 of bibliography 4, specific synthesis route is as follows：
Its main raw material is compounds Ⅳ -4~IV -8 that embodiment 1 synthesizes, and other drugs and reagent are market pin
The product sold.
In room temperature N2Under protection, compounds Ⅳ -1,150mL absolute ethyl alcohols that 0.03mol embodiments 1 are provided add in
0.06mol tetraisopropoxy titaniums are pipetted in 250mL reaction flasks, after stirring and dissolving to be added in flask.Close N2Valve is passed through, is changed
To be passed through ammonia into reaction system, the N in reaction bulb is replaced2After 10min, then reaction flask is closed, ammonia is continually fed into,
And reaction unit is connected on U-shaped mercury gage, the pressure of ammonia is maintained in 20mmHg or so；It is stirred to react 12h, TLC
Monitor (ethyl acetate：Petroleum ether：Methanol (V:V:V=10:10:3) after) the reaction was complete, stop logical ammonia.
Reducing agent sodium borohydride 45mmol is added in into reaction bulb, generates a large amount of bubbles in reaction solution, the reaction was continued 3h.Add
Entering the ammonium hydroxide of the 2mol/L of 120mL quenches reaction, filters, and filtrate decompression concentration removes ethyl alcohol, filter cake ethyl acetate 150mL
Washing, ethyl acetate merges with the filtrate after concentration to be filtered again, and aqueous layer with ethyl acetate (200mL × 2) extracts after liquid separation, closes
And organic layer, with 300mL saturated common salt water washings, filtered after being dried over anhydrous sodium sulfate, be concentrated to give product, through recrystallizing methanol
Obtain III -1 white powdery solids 7.8g.Yield：72.9%；m.p.252-254℃；State：Clear crystal；1H NMR
(DMSO-d6,600MHz),δ(ppm)：1.32-2.00(m,8H,4CH2), 2.89 (dt, J=12.5,3.2Hz, 1H, CH-N),
3.79 (d, J=2.1Hz, 1H, CH-SO2),7.27-7.42(m,3H,Ph-H),8.21(s,3H,NH2+NH)。
Bibliography 4：Miriyala B,Bhattacharyya S,Johh S.Chemoselective reductive
alkylation ofammoniawith carbonyl compounds:synthesis ofprimary and
symmetrical secondary amines.Tetrahedron,2004,60:1463-1471.
It synthesizes to obtain other 7 N- (2- trifluoromethyl-4-chlorophenyls) -2- aminocycloalkyl sulphonyl according to above-mentioned method
Amine III -2~III -8, the physicochemical data of compound III -2~III -8 are shown in Table 3, and spectral data is shown in Table 4.
The physicochemical property and yield of 3 compound III -2~III -8 of table
The nuclear magnetic resonance spectroscopy and infrared spectrum of 4 compound III -2~III -8 of table
Embodiment 3
The preparation method and its characterization of compound I-1~I-60
Compound III -2~III -8 that the primary raw material of prepare compound I-1~I-60 is provided for embodiment 2, other drugs
And reagent is the product of market sale.
Specific synthesis route is as follows：
Specifically synthetic method is：Gas circuit is connected first, is passed through N2To drive the air in reaction bulb away, holding is passed through N2, in room
Under temperature, using the DMF of 10mL dryings as solvent, the 4A molecular sieves of 0.5g dryings, the cesium hydroxide addition flask of 2mmol dryings
In, stirring adds in the compound that the embodiment 2 of 1.5mmol provides after ten minutes, stirs after twenty minutes, after sulphonyl amine solvent,
1.8mmol halides are slowly added dropwise, are stirred to react 6-10 hours, is terminated and reacted according to TLC monitoring results.
Decompression filters later, and filtrate adds in the distilled water of 100mL, is transferred in separatory funnel and is extracted with the ether of 100mL × 3
It takes, combined ether layer is simultaneously dried with anhydrous sodium sulfate, is filtered, is then concentrated, obtain crude product.Crude by column chromatography (oil
Ether：Ethyl acetate=10：1) sterling is obtained.
It synthesizes according to the method described above and obtains 2- substituted-amino naphthene sulfamide amine, totally 60.The physics and chemistry number of these compounds
According to being shown in Table 5, nuclear magnetic resonance data is shown in Table 6.
The structure of 5 chemical compounds I -1~I -60 of table and physicochemical property and yield
The nuclear magnetic resonance spectroscopy and ir data of 6 chemical compounds I -1~I -60 of table
Embodiment 4
The bactericidal activity of -60 pairs of ash arrhizus bacterias of chemical compounds I -1~I
Specific method measures mycelial growth inhibition rate using flat band method, uses with reference to farm-chemical indoor determination test rule
The pastille culture medium of a concentration of 50mg/L measures target compound I -1~I -60 respectively to gathering and processing a variety of tomatoes of different regions
The bactericidal activity of ash arrhizus bacteria.Using carbendazim and procymidone as comparison medicament, setting acetone solvent is blank control, each to handle
In triplicate.After the bacterium colony in blank control is fully grown, the colony diameter of each processing is measured with crossing method, takes it flat
Mean value calculates inhibiting rate with the following formula：
Inhibiting rate (%)=(blank control colony diameter-drug containing medium colony diameter)/(blank control colony diameter-bacterium
Cake diameter) × 100%
Ash arrhizus bacteria is there is multiple biological strains, because living environment and the difference of drug level, gather and process different regions
Bacterial strain be also different to the sensibility of noval chemical compound.Determine all noval chemical compounds to CY-09 (picking up from Chaoyang),
The inhibitory activity of DL-11 (picking up from Dalian) and HLD-15 (picking up from Liaoning Huludao City) 3 kinds of botrytis cinereas are specific to test
It the results are shown in Table 7.
Inhibiting rate (the 50mg/ of table 7 chemical compounds I -1~I -60 couple of graw mold of tomato bacteria strain CY-09, HLD-15 and DL-11
L)
The result shows that -60 pairs of 3 kinds of grey mold bacterial strains of chemical compounds I -1~I prepared in embodiment 3 show it is higher
Bactericidal activity, generally higher than comparison medicament carbendazim and procymidone.Wherein, chemical compounds I -24, I -38, I -39, I -40, I -41,
I -44, I -45, I -46, I -47, I -48, I -49, I -50, I -54, I -55, I -56 inhibiting rate is higher than 80%.
Embodiment 5
The accurate toxicity test of -56 pairs of ash arrhizus bacterias of chemical compounds I -24, I -54, I -55, I
With reference to farm-chemical indoor determination test rule, using flat band method (inhibiting mycelia growth experiment), by sample chemical combination
5000,1250,312.5,78.25mg/L 4 original concentrations are made with acetone respectively in object.Under germ-free condition, with PDA (potatos
Dextrose culture-medium) dilution 100 times obtain the pastille culture medium of 50,12.5,3.125,0.7825mg/L 4 concentration.With rotten mould
Profit, pyrimethanil, cyprodinil, Boscalid and carbendazim are comparison medicament.The fungus block of diameter 6mm is inoculated with, in 23 DEG C or so trainings
It supports 3-5 days.Colony diameter (crossing method) is measured, using EXCEL softwares according to the statistics side of document (Liu Xia, etc. 2009)
Method calculates EC50Value, compares medicine virulence size.4 2- substituted amido cyclohexyl sulfamide compounds pair prepared by embodiment 3
The EC of the toxicity test of 3 kinds of ash arrhizus bacteria Botrytis cinerea508 are shown in Table, bacterial strain code name is respectively that CY-09 (picks up from Liaoning
Towards the sunlight), DL-11 (picking up from Dalian), HLD-15 (picking up from Liaoning Huludao City).
84 kinds of compounds of table are to the virulence (EC of 3 kinds of ash arrhizus bacterias50,mg/L)
| Compound | Grey mold CY-09 | Grey mold DL-11 | Grey mold HLD-15 |
| Ⅰ-24 | 3.17 | 2.37 | 1.41 |
| Ⅰ-54 | 2.54 | 3.03 | 1.13 |
| Ⅰ-55 | 2.63 | 2.74 | 3.04 |
| Ⅰ-56 | 1.99 | 1.26 | 0.86 |
| Pyrimethanil | 7.12 | 11.57 | 15.36 |
| Cyprodinil | 3.582 | 2.58 | 6.79 |
| Procymidone | 10.31 | 3.88 | 6.03 |
| Boscalid | 4.46 | 5.56 | 7.88 |
| Carbendazim | 867.83 | 6550.50 | 733.72 |
Result of the test shows 4 2- substituted amido cyclohexyl sulfamide compounds of the preparation of embodiment 3 to 3 kinds of diseases
Opportunistic pathogen has very high bactericidal activity.From EC50Value sees that the activity of -56 pairs of 3 kinds of pathogens of chemical compounds I -24, I -54, I -55, I is
Higher than the EC of comparison medicament pyrimethanil, Boscalid, procymidone and carbendazim, wherein compound 5650Value is in 0.86-1.99mg/
L。
Meanwhile above-mentioned result of the test is also shown that when connection substitution acetamide and substituted benzyl, compound activity are general on amido
All over higher, and two substitution activity on benzyl, higher than monobasic activity, result of the test also found that the activity of substitution phenethyl is high
In substituted benzyl and substitution phenylpropyl；When connecting alkyl and substituted carboxylic ester on amido, compound activity is slightly worse.With 2-
Chloro- 5 5-chloromethyl thiazole and different 2- aminocycloalkyls sulfonamide are to the 2- substituted thiazole amido cyclohexyl sulphonyl that is bonded into
Aminated compounds has very high bactericidal activity, generally higher than comparison medicament.It lives from chemical compounds I -24, I -48, I -49 sterilization
Property can be seen that the size of cycloalkyl has bactericidal activity large effect, wherein the active highest of hexa-atomic cyclics,
When substituted base on hexatomic ring, compound activity is larger with the size of substituent group and the position difference of substituent group, works as substitution
Base is methyl and at 4-, substituent group activity highest.
Embodiment 6
The bactericidal activity of -60 pairs of 6 kinds of plant pathogenic fungis of chemical compounds I -1~I
With reference to farm-chemical indoor determination test rule, using flat band method (inhibiting mycelia growth experiment), use is a concentration of
The pastille culture medium of 50mg/L measures target compound 1-60 to Rhizoctonia solani Kuhn, rice blast fungus, the leaf blight of corn
Bacterium, Cochliobolus sativus, Fusarium oxysporum, capsicum epidemic disease germ bactericidal activity.Using procymidone, carbendazim as comparison medicine
Agent, setting acetone solvent are blank control, and each processing is in triplicate.After the bacterium colony in blank control is fully grown, with ten
Word interior extrapolation method measures the colony diameter of each processing, takes its average value, calculates inhibiting rate with the following formula, result of the test is shown in Table 9.
Inhibiting rate (%)=(blank control colony diameter-drug containing medium colony diameter)/(blank control colony diameter-bacterium
Cake diameter) × 100%
The inhibitory activity (50mg/L) of table -1~I -60 pair of 6 kinds of pathogen of 9 chemical compounds I
The result shows that chemical compounds I -1~I -60 prepared by embodiment 3 has bactericidal activity to this 6 kinds of pathogens, it is most of
Compound to the activity of rice blast fungus higher than comparison medicament procymidone, wherein chemical compounds I -24, I -54, I -55, I -56, I -
The inhibiting rate of 57 pairs of rice blast fungus reaches 100%；In addition, majority of compounds is to melon withered, capsicum epidemic disease and wheat
Pine root fungus has higher activity, but slightly worse to the inhibition of rice banded sclerotial blight and Exserohilum turcicum.
Embodiment 7
The Herbicidal of chemical compounds I -1~I -60
With reference to farm-chemical indoor determination test rule (the Institute for the Control of Agrochemicals of the Ministry of Agriculture,PRC, 2008), change prepared by embodiment 3
The acetone soln that object is configured to a concentration of 1000mg/L is closed, the addition of 0.5mL liquids is drawn and is covered in the 6cm culture dishes of filter paper, treat
After acetone volatilization is dry, 0.05% Tween 80 aqueous solutions of 5mL are added in, dilution obtains the aqueous solution of 100mg/L, then will just sprout
The seed of hair is fitly arranged in culture dish, is placed in 23-26 DEG C of environment and is cultivated, using 0.05% Tween 80 aqueous solution as sky
White control, often handles 3 repetitions.After 3-6 days, monocotyledon weed barnyard grass, lady's-grass are measured respectively (using isoconcentration Acetochlor as control
Medicament) and broadleaf weed Amaranthus retroflexus, the bud of piemarker (using isoconcentration atrazine as comparison medicament) are long and root long, calculating weeding are lived
Property, formula is as follows：
Inhibiting rate (%)=(blank control length-treated length)/blank control length × 100%
The activity of weeding experimental result of chemical compounds I -1~I -60 is shown in Table 10.
The activity of weeding (100mg/L) of 10 chemical compounds I -1~I -60 of table
It can be seen that inhibition ratios of the compound 1-60 to broadleaf weed of the preparation of embodiment 3 by above-mentioned data
Monocotyledonous good, compound 3 has good inhibiting effect to the bud and root of barnyard grass, higher than comparison medicament Acetochlor, compound
I -2, I -4, I -47, I -48 pair of barnyard grass is followed by good inhibitory activity.Chemical compounds I -46 and I -57 can significantly inhibit lady's-grass
Bud and root growth, inhibiting rate are higher than Acetochlor, in addition, chemical compounds I -24, I -38, I -54, I -55, I -56, I -57 pair of lady's-grass
Bud growth has obvious inhibiting effect.
To Shuangzi weeds Amaranthus retroflexus and piemarker experiments have shown that：Chemical compounds I -2, I -3, I -10, I -13, I -14, I -16, I -
24th, I -30, I -40, I -41, I -42, I -47, I -48, I -55, I -56, I -58 can significantly inhibit Amaranthus retroflexus bud and root life
Long, effect is superior to atrazine；Majority of compounds shows good inhibition to the bud and root growth of piemarker, changes
Conjunction object I -9, I -16, I -24, I -32, I -34, I -35, I -37, I -39, I -40, I -42, I -43, I -44, I -45, I -46, I -
47th, the root of I -50, I -59 pair of piemarker and bud growth inhibitory activity are superior to atrazine.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, and protection domain is unlimited
In this.The equivalent substitute or transformation that those skilled in the art are made on the basis of the present invention, the protection in the present invention
Within the scope of, protection scope of the present invention is subject to claims.
Claims (8)
1. a kind of 2- substituted-aminos naphthene sulfamide amine compounds, which is characterized in that there is the structure as shown in formula (I),
Wherein：R1Selected from H, 4-CH3-、5-C2H5-、5-n-C3H7-、5-n-C5H11In any one；
R2Selected from CH2=CHCH2-、CH3(CH2)2-、CH3(CH2)3-、CH3(CH2)4-、C6H5CH2-、4-CH3C6H4-CH2-、3-
CH3C6H4-CH2-、4-BrC6H4-CH2-、3-FC6H4-CH2-、2-CH3C6H4-CH2-、4-FC6H4-CH2-、2-FC6H4-CH2-、4-
CF3OC6H4-CH2-、2-Cl-5-FC6H3-CH2-、2-BrC6H4-CH2-、3-ClC6H4-CH2-、4-CNC6H4-CH2-、4-
NO2C6H4-CH2-、4-FC6H4-(CH2)2-、C6H5(CH2)2-、4-NO2C6H4-(CH2)2-、C6H5(CH2)3-、CH3CH2COOCH2-、
CH3COOCH2-、CH3CH2COOCH(CH3)-、CH3COOCH(CH3)-、2-CH3C6H4NHCO-CH2-、4-FC6H4NHCO-CH2-、4-
CH3OC6H4NHCO-CH2-、C6H5NHCO-CH2-、3-BrC6H4NHCO-CH2-、3-FC6H4NHCO-CH2-、3-CH3OC6H4NHCO-
CH2-、3-CF3C6H4NHCO-CH2-、2-CF3OC6H4NHCO-CH2-、2-BrC6H4NHCO-CH2-、2,5-2FC6H3NHCO-CH2-、
2,4-2FC6H3NHCO-CH2-、3-F-4-Br-C6H3NHCO-CH2-、2-F-4-Br-C6H3NHCO-CH2-、3,5-
2CF3C6H3NHCO-CH2-、2-CF3-4-F-C6H3NHCO-CH2-、2-F-4-Cl-C6H3NHCO-CH2-、3-CN-4-F-
C6H3NHCO-CH2-、2-CF3C6H4NHCO-CH2-、3,4-2FC6H3NHCO-CH2-、2,4,5-3FC6H2NHCO-CH2-、2,3,4-
3FC6H2NHCO-CH2-、3-CF3C6H4-CH2NHCO-CH2-、2-CH3C6H4-CH2NHCO-CH2-、2-CH3OC6H4-CH2NHCO-
CH2In any one；M is selected from 1,2 or 3.
2. 2- substituted-aminos naphthene sulfamide amine compounds according to claim 1, which is characterized in that the compound choosing
One kind from following structural formula:
3. a kind of preparation method of 2- substituted-aminos naphthene sulfamide amine compounds as described in claim 1, which is characterized in that
The synthetic route of formula (I) compound represented is：
In formula (II)-(V), R1And R2Definition with claim 1；
Specifically synthetic method is：
Using the cyclanone shown in formula (V) as raw material, sulfonated reaction generation, chlorination reaction, aminating reaction production (IV) are shown
2- keto naphthene sulfamide amine compounds；
Again using the 2- keto naphthene sulfamides amine compounds shown in formula (IV) as raw material, formula (III) institute is synthesized through reduction amination
The 2- aminocycloalkyl sulfonamide compounds shown；
Again using the 2- aminocycloalkyls sulfonamide compounds shown in formula (III) as raw material, with the alkylating reagent shown in formula (II) into
Row reaction, obtains the 2- substituted-amino naphthene sulfamide amine compounds shown in formula (I).
It is 4. a kind of such as the purposes of claim 1-2 any one of them 2- substituted-amino naphthene sulfamide amine compounds, feature
It is, as agricultural bacteriocide.
5. the purposes of 2- substituted-aminos naphthene sulfamide amine compounds according to claim 4, which is characterized in that for killing
Go out tomato gray mould, rice banded sclerotial blight, rice rice blast, the big spot of corn, Root Rot of Wheat, it is melon it is withered, in Phytophthora capsici one
Kind is a variety of.
It is 6. a kind of such as the purposes of claim 1-2 any one of them 2- substituted-amino naphthene sulfamide amine compounds, feature
It is, as agriculture herbicide.
7. the purposes of 2- substituted-aminos naphthene sulfamide amine compounds according to claim 6, which is characterized in that for agriculture
The prevention of field monocotyledon weed and broadleaf weed.
8. a kind of herbicide, which is characterized in that main component is claim 1-2 any one of them 2- substituted-amino cycloalkyl
Sulfonamide compounds.
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