CN105294598A - Isolongifolene[1,2,3]thiadiazole compound and preparation method and application thereof - Google Patents
Isolongifolene[1,2,3]thiadiazole compound and preparation method and application thereof Download PDFInfo
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- CN105294598A CN105294598A CN201510823705.8A CN201510823705A CN105294598A CN 105294598 A CN105294598 A CN 105294598A CN 201510823705 A CN201510823705 A CN 201510823705A CN 105294598 A CN105294598 A CN 105294598A
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- isolongifolenone
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- JLZSNUIUUSVFHM-UHFFFAOYSA-N CC(C)(C(CC1)CC11C2(C)C)C1=Cc1c2[s]nn1 Chemical compound CC(C)(C(CC1)CC11C2(C)C)C1=Cc1c2[s]nn1 JLZSNUIUUSVFHM-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/14—Thiadiazoles; Hydrogenated thiadiazoles condensed with carbocyclic rings or ring systems
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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
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses an isolongifolene[1,2,3]thiadiazole compound and a preparation method and an application thereof. The synthesis method comprises the steps: carrying out condensation of isolongifolenone with semicarbazide hydrochloride to generate isolongifolenone semicarbazide, then carrying out condensation cyclization with sulfoxide chloride to obtain the isolongifolene[1,2,3]thiadiazole compound, namely 5,5,9,9-tetramethyl-5,6,7,8,8a,9-hexahydro-6,8a-bridged methylene-1,2,3-naphthothiadiazole. The isomerized product isolongifolenone of natural renewable resource heavy turpentine is used as a raw material for preparation of the novel isolongifolene[1,2,3]thiadiazole compound 5,5,9,9-tetramethyl-5,6,7,8,8a,9-hexahydro-6,8a-bridged methylene-1,2,3-naphthothiadiazole. Researches confirm that the compound can be used as an insecticide and has specific toxic killing effect on diamond back moth.
Description
Technical field
The invention belongs to technical field of organic synthesis.Relate to a kind of Isolongifolene base [1,2,3] thiadiazole compound and its preparation method and application.
Background technology
Small cabbage moth belongs to lepidopteran diamond-back moth section, is the worldwide insect that migrates, the cress such as main harm wild cabbage, purple cabbage, broccoli, a kind of sedge dish, leaf mustard, Cauliflower, Chinese cabbage, rape, radish.Harm characteristics is: first instar larvae only takes food mesophyll, leaves epidermis, dish leaf forms spot transparent one by one, blank, and dish leaf can be eaten into hole and incise by 3 ~ 4 instar larvaes, and time serious, full leaf is eaten and reticulated.Often concentrate lobus cardiacus to cause harm in seedling stage, affect the bag heart.Reserving seed for planting in strain, endangering tender stem, young pod and seed.
A lot of method is existed to the prevention and controls of small cabbage moth, such as cultural control, physical control, biological control and medical treatment etc.Cultural control requires to avoid the continuous cropping of crop anniversary, in order to avoid go round and begin again in worm source, although this method is effective, greatly reduces economic benefit; Physical control utilizes the phototaxis of small cabbage moth, sends out period worm, and by placing black light lamps small cabbage moth, although the economic environmental protection of this method, insecticide efficiency is low, can not effectively pest control; Biological control mainly adopts biotic pesticide such as BT emulsion to prevent and treat small cabbage moth, this method high-efficiency environment friendly safety, but technical requirements is higher, if use improper, can reduce drug effect even invalid.Chemical control mainly contains ten thousand spirits, SD-1750 etc., and this method effectively can kill small cabbage moth, but can produce key, and easily " burning leaf "; In addition, the sterilant complex synthetic route of some high-efficiency environment friendlies, cost is higher.
The present invention's a kind of novel Isolongifolene base [1 that utilizes Isolongifolene to be Material synthesis, 2,3] thiadiazole compound, and have studied its virulence effect to small cabbage moth, it has efficiently as sterilant, environmental protection, the feature such as easy to use, and synthetic route is simple, with low cost, be expected to use as novel pesticide.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of the present invention is to provide a kind of Isolongifolene base [1,2,3] thiadiazole compound.Another object of the present invention is to provide the synthetic method of above-mentioned Isolongifolene base [1,2,3] thiadiazole compound.The present invention also has an object to be to provide the application of above-mentioned Isolongifolene base [1,2,3] thiadiazole compound.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is:
Isolongifolene base [1,2,3] thiadiazole compound, structural formula is:
The synthetic method of described Isolongifolene base [1,2,3] thiadiazole compound: come into leaves ketenes and carbamylhydrazine hydrochloride carry out condensation, obtain Isolongifolenone semicarbazone; Isolongifolenone semicarbazone and sulfur oxychloride carry out condensation and cyclization, obtain 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles.Reaction formula is as follows:
The synthetic method of described Isolongifolene base [1,2,3] thiadiazole compound, Isolongifolenone and carbamylhydrazine hydrochloride carry out condensation, obtain Isolongifolenone semicarbazone, and concrete preparation method comprises:
1) 0.02mol Isolongifolenone, 0.02mol carbamylhydrazine hydrochloride, 0.02mol sodium acetate, 60mL ethanol and 20mL water are added in the there-necked flask being furnished with agitator, thermometer and reflux exchanger successively, back flow reaction 8h under nitrogen protection, with TLC tracing detection until Isolongifolenone almost react completely after stopped reaction;
2) reactant suction filtration obtains white solid, i.e. Isolongifolenone semicarbazone crude product;
3) Isolongifolenone semicarbazone crude product carries out recrystallization in acetone-ethanol solvent, obtains Isolongifolenone semicarbazone sterling, is white powdery solids.
The synthetic method of described Isolongifolene base [1,2,3] thiadiazole compound, Isolongifolenone semicarbazone and sulfur oxychloride carry out condensation and cyclization, obtain 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles, concrete preparation method comprises:
1) 0.01mol Isolongifolenone semicarbazone, 25mL sulfur oxychloride and 30mL methylene dichloride are added in the there-necked flask being furnished with agitator, thermometer and reflux exchanger successively, under condition of ice bath, react normal-temperature reaction 7h after 1h;
2) reaction mixture 0.10-0.30L saturated sodium bicarbonate solution neutralization, with 0.15-0.30L dichloromethane extraction 3 times, combining extraction liquid, is washed with distilled water to neutrality, then uses saturated common salt water washing 1 time, and organic phase anhydrous sodium sulfate drying anhydrates part; Concentration and recovery solvent after filtration removal siccative, obtains 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles crude product;
3) 5,5,9,9-tetramethyl-s-5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles crude on silica gel post is separated, and eluent is sherwood oil: ethyl acetate=3:1, obtains weak yellow liquid, and underpressure distillation is except desolventizing, obtain faint yellow solid, be 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles sterling.
Described Isolongifolene base [1,2,3] thiadiazole compound is preparing the application in sterilant.Described worm is small cabbage moth.
Beneficial effect: compared with prior art, the present invention for raw material, carries out condensation with carbamylhydrazine hydrochloride with the oxidation products Isolongifolenone of natural reproducible resource Isolongifolene, obtains Isolongifolenone semicarbazone; Isolongifolenone semicarbazone carries out condensation and cyclization with sulfur oxychloride again, obtains 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles.Research find this compound to 3 mid-term in age diamondback moth larvae there is good toxicity action, and virulence and concentration present linear relationship, y=2.1797+1.8048x, and its Toxicity Determination result to small cabbage moth shows LC
50value and 95% confidence are limited to 36.528 (25.770-48.530) (mga.i./L).This compound can be used as specificity insecticidal active compound and applies in sterilant.
Accompanying drawing explanation
Fig. 1 is 5,5,9,9-tetramethyl--5,6,7,8,8 α of different concns, and 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles is to small cabbage moth Toxicity Determination variation relation result figure.
Specific implementation method
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
The synthetic method of Isolongifolene base [1,2,3] thiadiazole compound, detailed process is as follows:
1) in the 100mL there-necked flask being furnished with thermometer, agitator and condenser, add 0.02mol Isolongifolenone, 0.02mol carbamylhydrazine hydrochloride, 0.02mol sodium acetate, 60mL ethanol and 20mL water successively, be heated to reflux temperature reaction 8h, with TCL tracing detection until Isolongifolenone almost react completely after stopped reaction.Reactant suction filtration obtains white solid, i.e. Isolongifolenone semicarbazone crude product, then carries out recrystallization with 10mL acetone-ethanol solvent, obtains Isolongifolenone semicarbazone, is white powdery solids, and yield is 92%, 217.4 ~ 218.2 DEG C; IR (KBr, cm
-1): 3458.7,3218.5,2959.0,2920.6,2869.4,1680.4,1639.5,1565.8,1472.9,1303.2,1123.8,1082.2;
1hNMR (DMSO, 300MHz) δ: 9.10 (s, 1H ,-NH-), 6.23 (s, 2H ,-NH
2), 5.72 (s, 1H ,=CH-), alkyl: 2.50 (s, 2H ,-CH
2), 1.86 (m, J=12Hz, 2H ,-CH
2), 1.69 (t, J=12Hz, 2H ,-CH
2), 1.52 (d, J=6Hz, 2H ,-CH
2), 1.31 (m, J=9Hz, 2H ,-CH
2), 1.07 (s, 3H ,-CH
3), 1.01 (s, 6H ,-CH
3), 0.81 (s, 3H ,-CH
3).
2) in the 100mL there-necked flask being furnished with thermometer, agitator and condenser, add 0.01mol Isolongifolenone semicarbazone, 25mL sulfur oxychloride and 30mL methylene dichloride successively, after being placed in ice bath stirring reaction 1h, remove ice bath, stirring at normal temperature 7h, use TCL tracing detection, to product no longer increases.Reaction mixture 0.10-0.30L saturated sodium bicarbonate solution neutralization, with 0.15-0.30L dichloromethane extraction 3 times, combining extraction liquid, is washed with distilled water to neutrality, then uses saturated common salt water washing 1 time, and organic phase anhydrous sodium sulfate drying anhydrates part; Concentration and recovery solvent after filtration removal siccative, obtains 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles crude product; Be separated through silicagel column, eluent is sherwood oil: ethyl acetate=3:1, obtains weak yellow liquid, and underpressure distillation is except desolventizing, obtain faint yellow solid, be 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles, yield is 42%, 83.4 ~ 83.9 DEG C; IR (KBr, cm
-1): 2964.7,2866.7,1649.5,1574.7,1543.5,1460.8,1385.7,1363.3,1218.0,871.0,847.2;
1hNMR (DMSO, 300MHz) δ: 6.65 (s, 1H ,=CH-), alkyl: 1.83 ~ 1.87 (m, J=12Hz, 2H ,-CH
2), 1.73 ~ 1.78 (t, J=15Hz, 2H ,-CH
2), 1.55 ~ 1.62 (d, J=21Hz, 2H ,-CH
2), 1.51 (s, 3H ,-CH
3), 1.47 ~ 1.40 (m, J=21Hz, 1H ,-CH), 1.20 (s, 3H ,-CH
3), 1.06 ~ 1.11 (s, 6H ,-CH
3).
Isolongifolene base [1,2,3] thiadiazole compound, is: 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles, and structural formula is:
Embodiment 3
Supply examination insect to be small cabbage moth (Plutellaxyllostella (Linnaeus)), in June, 2013 is presented by pesticide molecules toxicity seminar of plant protection institute of Agricultural University Of Nanjing, is the sensitive strain in indoor feeding many generations.
The Toxicity Determination of small cabbage moth adopts leaf dipping method.Former medicinal acetone to be measured is mixed with the mother liquor of high density, 200mg/L is diluted to the 0.1%TritonX-100 aqueous solution during Primary Screening Test, virulence line is diluted to required series concentration gradient with the 0.1%TritonX-100 aqueous solution when measuring, the cabbage leaf dish of diameter 5cm is soaked 10s respectively in above-mentioned liquid, naturally dry to without open fire after taking out, with the 0.1%TritonX-100 aqueous solution for contrast.The leaf butterfly of drying is put into the plastic culture dish of diameter 6.5cm, access of the same size 3 mid-term in age diamondback moth larvae 10.The each process of Primary Screening Test repeats for 3 times, and virulence line determination test establishes 5 process, often processes 4 times and repeats.Small cabbage moth after process is put into the constant incubator that temperature is 25 ± 1 DEG C, the photoperiod is 16h:8h (L:D) and cultivates, and connects check result after worm 48h.Touch polypide with writing brush during inspection, with larva can not coordinated movement for death standard.
Table 1 compound (I) records table to the toxicity primary dcreening operation raw data of small cabbage moth
5,5,9,9-tetramethyl--5,6,7,8,8a, 9-six the virulence line of hydrogen-6,8a-endo-methylene group-1,2,3-naphtho-thiadiazoles (compound (I)) measure with U.S. EPA computed in software toxicity regression formula, LC
50value and 95% fiducial limit.
Table 2 compound (I) records table to small cabbage moth Toxicity Determination raw data
Result is as shown in table 1, table 2 and Fig. 1.Virulence regression equation Y=2.1797+1.8048X, LC
50value is that 36.528,95% confidence is limited to 25.770-48.530mga.i./L.This compound visible can be used as specificity insecticidal active compound, has a wide range of applications in sterilant.
Claims (6)
1. Isolongifolene base [1,2,3] thiadiazole compound, is characterized in that, the structural formula of this compound is:
2. the synthetic method of Isolongifolene base [1,2, the 3] thiadiazole compound of claim 1, is characterized in that: come into leaves ketenes and carbamylhydrazine hydrochloride carry out condensation, obtain Isolongifolenone semicarbazone; Isolongifolenone semicarbazone and sulfur oxychloride carry out condensation and cyclization, obtain 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles.
3. the synthetic method of Isolongifolene base according to claim 2 [1,2,3] thiadiazole compound, is characterized in that: Isolongifolenone and carbamylhydrazine hydrochloride carry out condensation, obtain Isolongifolenone semicarbazone, and concrete preparation method comprises:
1) 0.02mol Isolongifolenone, 0.02mol carbamylhydrazine hydrochloride, 0.02mol sodium acetate, 60mL ethanol and 20mL water are added in the there-necked flask being furnished with agitator, thermometer and reflux exchanger successively, back flow reaction 8h under nitrogen protection, with TLC tracing detection until Isolongifolenone almost react completely after stopped reaction;
2) reactant suction filtration obtains white solid, i.e. Isolongifolenone semicarbazone crude product;
3) Isolongifolenone semicarbazone crude product carries out recrystallization in acetone-ethanol solvent, obtains Isolongifolenone semicarbazone sterling, is white powdery solids.
4. the synthetic method of Isolongifolene base according to claim 2 [1,2,3] thiadiazole compound, it is characterized in that: Isolongifolenone semicarbazone and sulfur oxychloride carry out condensation and cyclization, obtain 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles, concrete preparation method comprises:
1) 0.01mol Isolongifolenone semicarbazone, 25mL sulfur oxychloride and 30mL methylene dichloride are added in the there-necked flask being furnished with agitator, thermometer and reflux exchanger successively, under condition of ice bath, react normal-temperature reaction 7h after 1h;
2) reaction mixture 0.10-0.30L saturated sodium bicarbonate solution neutralization, with 0.15-0.30L dichloromethane extraction 3 times, combining extraction liquid, is washed with distilled water to neutrality, then uses saturated common salt water washing 1 time, and organic phase anhydrous sodium sulfate drying anhydrates part; Concentration and recovery solvent after filtration removal siccative, obtains 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles crude product;
3) 5,5,9,9-tetramethyl-s-5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles crude on silica gel post is separated, and eluent is sherwood oil: ethyl acetate=3:1, obtains weak yellow liquid, and underpressure distillation is except desolventizing, obtain faint yellow solid, be 5,5,9,9-tetramethyl--5,6,7,8,8 α, 9-six hydrogen-6,8 α-endo-methylene group-1,2,3-naphtho-thiadiazoles sterling.
5. Isolongifolene base [1,2, the 3] thiadiazole compound of claim 1 is preparing the application in sterilant.
6. application according to claim 5, is characterized in that: described worm is small cabbage moth.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106588772A (en) * | 2016-12-19 | 2017-04-26 | 广西中医药大学 | Heavy turpentine longifolene derivative, preparation thereof and application |
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| CN101801901A (en) * | 2007-07-13 | 2010-08-11 | 美国农业部 | Use Isolongifolene ketone and/or the arthropodan method of Isolongifolene keto analog repellent |
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| CN101801901A (en) * | 2007-07-13 | 2010-08-11 | 美国农业部 | Use Isolongifolene ketone and/or the arthropodan method of Isolongifolene keto analog repellent |
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| CN106588772A (en) * | 2016-12-19 | 2017-04-26 | 广西中医药大学 | Heavy turpentine longifolene derivative, preparation thereof and application |
| CN106588772B (en) * | 2016-12-19 | 2020-04-24 | 广西中医药大学 | Heavy turpentine longifolene derivative and preparation and application thereof |
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