CN105294598B - Isolonglifolene base [1,2,3] thiadiazole compound and its preparation method and application - Google Patents
Isolonglifolene base [1,2,3] thiadiazole compound and its preparation method and application Download PDFInfo
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- CN105294598B CN105294598B CN201510823705.8A CN201510823705A CN105294598B CN 105294598 B CN105294598 B CN 105294598B CN 201510823705 A CN201510823705 A CN 201510823705A CN 105294598 B CN105294598 B CN 105294598B
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- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
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- 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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Abstract
The invention discloses a kind of isolonglifolene base [1,2,3] thiadiazole compound and its preparation method and application.The synthetic method is：Isolongifolenone carries out condensation generation Isolongifolenone semicarbazones with semicarbazide hydrochloride, then obtains isolonglifolene base [1,2 with thionyl chloride progress condensation and cyclization, 3] thiadiazole compound --- 5,5,9,9 tetramethyls 5,6,7,8,8a, 9 hexahydros 6,8a endo-methylene groups 1,2,3 naphtho- thiadiazoles.The present invention prepares new isolonglifolene base [1,2,3] thiadiazole compound 5 using the isomerization product Isolongifolenone of natural reproducible resource heavy turpentine for raw material, 5,9,9 tetramethyls 5,6,7,8,8a, 9 hexahydros 6,8a endo-methylene groups 1,2,3 naphtho- thiadiazoles, confirm that the compound can have selectivity toxic effect to diamondback moth as insecticide through research.
Description
Technical field
The invention belongs to technical field of organic synthesis.Be related to a kind of isolonglifolene base [1,2,3] thiadiazole compound and its
Preparation method and application.
Background technology
Diamondback moth belongs to lepidoptera diamond-back moth section, is the worldwide insect that migrates, main harm wild cabbage, violet cabbage, broccoli, a kind of sedge
The crucifers such as dish, leaf mustard, cauliflower, Chinese cabbage, rape, radish.Harm characteristics are：First instar larvae only takes food mesophyll, leaves
Epidermis, forms spot transparent one by one, blank in dish leaf, and dish leaf can be eaten into hole and incised by 3~4 instar larvaes, sternly
Full leaf, which is eaten, during weight reticulates.Often concentrate lobus cardiacus to cause harm in seedling stage, influence core.Reserving seed for planting in strain, harm tender stem, young pod and seed
Grain.
There are many methods, such as cultural control, physical control, biological control and medicine to the prevention and controls of diamondback moth
Thing preventing and treating etc..Cultural control requirement avoids the continuous cropping of crop anniversary, in case worm sources are gone round and begun again, although this method effectively, drops significantly
Low economic benefit；Physical control utilizes the phototaxis of diamondback moth, during worm sends out, by placing black light lamps diamondback moth,
This method is although economic and environment-friendly, but insecticide efficiency is low, it is impossible to effective pest control；Biological control mainly uses biological insecticides
Such as BT emulsions are prevented and treated diamondback moth, this method high-efficiency environment friendly safety, but technical requirements are higher, if using improper, can drop
Low drug effect is even invalid.Chemical control mainly has ten thousand spirits, DDVP etc., and this method can effectively kill diamondback moth, but can produce key,
And easily " burning leaf "；In addition, the insecticide complex synthetic route of some high-efficiency environment friendlies, cost is higher.
The present invention is a kind of new isolonglifolene base [1,2,3] thiadiazole chemical combination of Material synthesis using isolonglifolene
Thing, and its virulence effect to diamondback moth, the features such as it has efficient, environmental protection, convenient use as insecticide are have studied, and close
It is simple into route, it is with low cost, it is expected to use as novel pesticide.
The content of the invention
Goal of the invention：For the deficiencies in the prior art, it is an object of the invention to provide a kind of isolonglifolene base
[1,2,3] thiadiazole compound.It is a further object of the present invention to provide above-mentioned isolonglifolene base [1,2,3] thiadiazole chemical combination
The synthetic method of thing.Further object of the present invention is to provide the application of above-mentioned isolonglifolene base [1,2,3] thiadiazole compound.
Technical scheme：In order to realize foregoing invention purpose, the technical solution adopted by the present invention is：
Isolonglifolene base [1,2,3] thiadiazole compound, structural formula is：
The synthetic method of described isolonglifolene base [1,2,3] thiadiazole compound：Come into leaves ketenes and semicarbazides hydrochloric acid
Salt is condensed, and obtains Isolongifolenone semicarbazones；Isolongifolenone semicarbazones carries out condensation and cyclization with thionyl chloride, obtains
To -6,8 α of 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydro-endo-methylene group -1,2,3- naphtho- thiadiazoles.Reaction equation is as follows：
The synthetic method of described isolonglifolene base [1,2,3] thiadiazole compound, Isolongifolenone and semicarbazides salt
Hydrochlorate is condensed, and obtains Isolongifolenone semicarbazones, and specific preparation method includes：
1) by 0.02mol Isolongifolenones, 0.02mol semicarbazide hydrochlorides, 0.02mol sodium acetates, 60mL ethanol and
20mL water is sequentially added in the three-necked flask equipped with agitator, thermometer and reflux condenser, under nitrogen protection back flow reaction
8h, is stopped reacting with TLC tracing detections after Isolongifolenone almost reacts completely；
2) reactant suction filtration obtains white solid, i.e. Isolongifolenone semicarbazones crude product；
3) Isolongifolenone semicarbazones crude product is recrystallized in acetone-ethanol solvent, obtains Isolongifolenone
Semicarbazones sterling, is white powdery solids.
The synthetic method of described isolonglifolene base [1,2,3] thiadiazole compound, Isolongifolenone semicarbazones with
Thionyl chloride carries out condensation and cyclization, obtains 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydros -6,8 α-endo-methylene group -1,2,
3- naphtho- thiadiazoles, specific preparation method includes：
1) 0.01mol Isolongifolenones semicarbazones, 25mL thionyl chlorides and 30mL dichloromethane are sequentially added and be furnished with
In the three-necked flask of agitator, thermometer and reflux condenser, normal-temperature reaction 7h after 1h is reacted under condition of ice bath；
2) reactant mixture is neutralized with 0.10-0.30L saturated sodium bicarbonate solutions, is extracted with 0.15-0.30L dichloromethane
3 times, combining extraction liquid is washed with distilled water to neutrality, then with saturated common salt water washing 1 time, organic phase is dry with anhydrous sodium sulfate
It is dry to remove moisture content；Filtering removes concentration and recovery solvent after drier, obtains 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydro -6,
8 α-endo-methylene group -1,2,3- naphtho- thiadiazoles crude products；
3) -6,8 α of 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydro-endo-methylene group -1,2,3- naphtho- thiadiazoles is slightly produced
Thing is through silica gel post separation, and eluant, eluent is petroleum ether:Ethyl acetate=3:1, weak yellow liquid is obtained, vacuum distillation removes solvent,
Obtain faint yellow solid, as 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydros -6,8 α-endo-methylene group -1,2,3- naphtho-s
Thiadiazoles sterling.
Application of described isolonglifolene base [1,2,3] thiadiazole compound in insecticide is prepared.Described worm is
Diamondback moth.
Beneficial effect：Compared with prior art, the present invention is with the different length of oxidation product of natural reproducible resource isolonglifolene
Leaf ketenes is raw material, is condensed with semicarbazide hydrochloride, obtains Isolongifolenone semicarbazones；Isolongifolenone semicarbazones
Condensation and cyclization is carried out with thionyl chloride again, 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydros -6,8 α-endo-methylene groups-is obtained
1,2,3- naphtho- thiadiazoles.Research finds that the compound has good toxicity action, and poison to 3 age mid-term diamondback moth larvaes
Power and concentration are presented linear relationship, y=2.1797+1.8048x, and its Toxicity Determination result to diamondback moth shows LC50Value
And 95% confidence be limited to 36.528 (25.770-48.530) (mg a.i./L).The compound can be used as selectivity insecticidal activity
Compound is applied in terms of insecticide.
Brief description of the drawings
Fig. 1 is -6,8 α of 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydro-endo-methylene group -1,2,3- of various concentrations
Naphtho- thiadiazoles is to diamondback moth Toxicity Determination variation relation result figure.
Specific implementation method
With reference to specific embodiment, the present invention is described further.
Embodiment 1
The synthetic method of isolonglifolene base [1,2,3] thiadiazole compound, detailed process is as follows：
1) in the 100mL three-necked flasks equipped with thermometer, agitator and condenser, sequentially add that 0.02mol is different to come into leaves
Ketenes, 0.02mol semicarbazide hydrochlorides, 0.02mol sodium acetates, 60mL ethanol and 20mL water, are heated to reflux temperature reaction 8h,
Stop reaction after Isolongifolenone almost reacts completely with TCL tracing detections.Reactant suction filtration obtains white solid, i.e., different length
Leaf ketenes semicarbazones crude product, then recrystallized with 10mL acetone-ethanol solvents, Isolongifolenone semicarbazones is obtained,
For white powdery solids, 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；1H NMR(DMSO,
300MHz)δ:9.10(s,1H,-NH-),6.23(s,2H,-NH2), 5.72 (s, 1H ,=CH-), alkyl：2.50(s,1H,-
), CH 1.86 (m, J=12Hz, 2H ,-CH2), 1.69 (t, J=12Hz, 2H ,-CH2), 1.52 (d, J=6Hz, 2H ,-CH2),
1.31 (m, J=9Hz, 2H ,-CH2),1.07(s,3H,-CH3),1.01(s,6H,-CH3),0.81(s,3H,-CH3)。
2) in the 100mL three-necked flasks equipped with thermometer, agitator and condenser, sequentially add that 0.01mol is different to come into leaves
Ketenes semicarbazones, 25mL thionyl chlorides and 30mL dichloromethane, are placed in ice bath after stirring reaction 1h, remove ice bath, normal temperature
7h is stirred, TCL tracing detections are used, untill product is not further added by.Reactant mixture is molten with 0.10-0.30L saturated sodium bicarbonates
Liquid is neutralized, and is extracted 3 times with 0.15-0.30L dichloromethane, combining extraction liquid is washed with distilled water to neutrality, then use saturated common salt
Water washing 1 time, organic phase removes moisture content with anhydrous sodium sulfate drying；Filtering removes concentration and recovery solvent after drier, obtains 5,5,
- 6,8 α of 9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydro-endo-methylene group -1,2,3- naphtho- thiadiazoles crude products；Through silicagel column point
From eluant, eluent is petroleum ether:Ethyl acetate=3:1, weak yellow liquid is obtained, vacuum distillation removes solvent, obtains pale yellow colored solid
Body, as 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydros -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；1H NMR(DMSO,300MHz)δ:6.65 (s, 1H ,=CH-), alkyl:
1.83~1.87 (m, J=12Hz, 2H ,-CH2), 1.73~1.78 (t, J=15Hz, 2H ,-CH2), 1.55~1.62 (d, J=
21Hz,2H,-CH2),1.51(s,3H,-CH3), 1.47~1.40 (m, J=21Hz, 1H ,-CH), 1.20 (s, 3H ,-CH3),
1.06~1.11 (s, 6H ,-CH3)。
Isolonglifolene base [1,2,3] thiadiazole compound, be：5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- six
Hydrogen -6,8 α-endo-methylene group -1,2,3- naphtho- thiadiazoles, structural formula is：
Embodiment 3
It is diamondback moth (Plutella xyllostella (Linnaeus)) for examination insect, in June, 2013 is by Nanjing agriculture
Pesticide molecules toxicity seminar of plant protection institute of university presents, and is the sensitive strain in indoor feeding many generations.
The Toxicity Determination of diamondback moth uses leaf dipping method.Active compound to be measured is configured to the mother liquor of high concentration, primary dcreening operation with acetone
200mg/L is diluted to during experiment with the 0.1%Triton X-100 aqueous solution, virulence line uses 0.1%Triton X-100 when determining
The aqueous solution is diluted to required series concentration gradient, and diameter 5cm cabbage leaf dish is soaked into 10s in above-mentioned decoction respectively, taken
Dried naturally after going out to without bright water, using the 0.1%Triton X-100 aqueous solution as control.The leaf butterfly dried is put into diameter
In 6.5cm plastic culture dish, 3 age mid-term diamondback moth larvae 10 of the same size is accessed.Primary Screening Test each handles 3 weights
Multiple, virulence line determination test sets 5 processing, often handles 4 repetitions.It is 25 ± 1 DEG C, light week that diamondback moth after processing, which is put into temperature,
Phase is 16h:8h(L:D cultivated in constant incubator), connect inspection result after worm 48h.Polypide is touched with writing brush during inspection, with children
Worm is unable to the coordinated movement of various economic factors for death standard.
The compound of table 1 (I) records table to the toxicity primary dcreening operation initial data of diamondback moth
5,5,9,9- tetramethyls -5,6,7,8,8a, 9- hexahydro -6,8a- endo-methylene group -1,2,3- naphtho- thiadiazoles (chemical combination
Thing (I)) virulence line determine and calculate toxicity regression formula, LC with U.S. EPA software50Value and its 95% confidence limit.
The compound of table 2 (I) records table to diamondback moth Toxicity Determination initial data
As a result as shown in table 1, table 2 and Fig. 1.Virulence regression equation Y=2.1797+1.8048X, LC50It is worth for 36.528,
95% confidence is limited to 25.770-48.530mg a.i./L.It can be seen that the compound can as selectivity insecticidal active compound,
Had a wide range of applications in terms of insecticide.
Claims (6)
- Isolonglifolene base 1. [1,2,3] thiadiazole compound, it is characterised in that the structural formula of the compound is：
- 2. the synthetic method of isolonglifolene base [1,2,3] thiadiazole compound of claim 1, it is characterised in that：It is different to come into leaves Ketenes is condensed with semicarbazide hydrochloride, obtains Isolongifolenone semicarbazones；Isolongifolenone semicarbazones and protochloride Sulfone carries out condensation and cyclization, obtains 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydros -6,8 α-endo-methylene group -1,2,3- naphtho-s Thiadiazoles.
- 3. the synthetic method of isolonglifolene base [1,2,3] thiadiazole compound according to claim 2, its feature exists In：Isolongifolenone is condensed with semicarbazide hydrochloride, obtains Isolongifolenone semicarbazones, specific preparation method bag Include：1) by 0.02mol Isolongifolenones, 0.02mol semicarbazide hydrochlorides, 0.02mol sodium acetates, 60mL ethanol and 20mL water Sequentially add in the three-necked flask equipped with agitator, thermometer and reflux condenser, under nitrogen protection back flow reaction 8h, use TLC tracing detections stop reaction after Isolongifolenone almost reacts completely；2) reactant suction filtration obtains white solid, i.e. Isolongifolenone semicarbazones crude product；3) Isolongifolenone semicarbazones crude product is recrystallized in acetone-ethanol solvent, obtains Isolongifolenone contracting ammonia Base urea sterling, is white powdery solids.
- 4. the synthetic method of isolonglifolene base [1,2,3] thiadiazole compound according to claim 2, its feature exists In：Isolongifolenone semicarbazones carries out condensation and cyclization with thionyl chloride, obtains 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- Hexahydro -6,8 α-endo-methylene group -1,2,3- naphtho- thiadiazoles, specific preparation method include：1) 0.01mol Isolongifolenones semicarbazones, 25mL thionyl chlorides and 30mL dichloromethane are sequentially added equipped with stirring In the three-necked flask of device, thermometer and reflux condenser, normal-temperature reaction 7h after 1h is reacted under condition of ice bath；2) reactant mixture is neutralized with 0.10-0.30L saturated sodium bicarbonate solutions, is extracted 3 times with 0.15-0.30L dichloromethane, Combining extraction liquid, is washed with distilled water to neutrality, then with saturated common salt water washing 1 time, organic phase is gone with anhydrous sodium sulfate drying Moisture content；Filtering removes concentration and recovery solvent after drier, obtains 5,5,9,9- tetramethyls -5,6,7,8,8 α, and 9- hexahydros -6,8 α - Endo-methylene group -1,2,3- naphtho- thiadiazoles crude products；3) -6,8 α of 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydro-endo-methylene group -1,2,3- naphtho- thiadiazoles crude product warp Silica gel post separation, eluant, eluent is petroleum ether:Ethyl acetate=3:1, weak yellow liquid is obtained, vacuum distillation removes solvent, obtained Faint yellow solid, as 5,5,9,9- tetramethyls -5,6,7,8,8 α, 9- hexahydros -6,8 α-endo-methylene group -1,2,3- naphtho-s thiophene two Azoles sterling.
- 5. application of isolonglifolene base [1,2,3] thiadiazole compound of claim 1 in insecticide is prepared.
- 6. application according to claim 5, it is characterised in that：Described worm is diamondback moth.
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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 |
| CN104892538A (en) * | 2015-06-16 | 2015-09-09 | 南京林业大学 | Isolongifolene alkyl oxazolone as well as synthesis method and application thereof |
| CN104892543A (en) * | 2015-06-03 | 2015-09-09 | 南京林业大学 | Thiazole compounds, as well as synthesis method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
| CN104892543A (en) * | 2015-06-03 | 2015-09-09 | 南京林业大学 | Thiazole compounds, as well as synthesis method and application thereof |
| CN104892538A (en) * | 2015-06-16 | 2015-09-09 | 南京林业大学 | Isolongifolene alkyl oxazolone as well as synthesis method and application thereof |
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| 异长叶烯酮的绿色合成;武法文等;《精细化工》;20091130;第26卷(第11期);第1116-1119页 * |
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Effective date of registration: 20181226 Address after: 225002 Chen Ci Village, Shatou Town, Guangling District, Yangzhou City, Jiangsu Province Patentee after: YANGZHOU YIYANG TECHNOLOGY DEVELOPMENT Co.,Ltd. Address before: No. 159, dragon pan Road, Nanjing, Jiangsu Patentee before: Nanjing Forestry University |
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Effective date of registration: 20220826 Address after: 225000 Lidian town science and Technology Pioneer Park, Guangling District, Yangzhou City, Jiangsu Province Patentee after: Yangzhou Shengning Information Technology Co.,Ltd. Address before: 225002 Chen Ci Village, Shatou Town, Guangling District, Yangzhou City, Jiangsu Province Patentee before: YANGZHOU YIYANG TECHNOLOGY DEVELOPMENT Co.,Ltd. |