CN103254171A - Aromatic heterocyclic triazine (trans)-delta-farnesene analogue and application thereof - Google Patents
Aromatic heterocyclic triazine (trans)-delta-farnesene analogue and application thereof Download PDFInfo
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Abstract
The invention relates to a method for preparing an aromatic heterocyclic triazine (trans)-delta-farnesene analogue (Formula I) and an application thereof in aphid control. The general structure of the compound is shown in the formula I, wherein R1 is pyridine, thiazole, phenyl, pyrazole, imidazole, oxazole, isoxazole, quinoline, thiophene, furan and tetrahydrofuran or halogen, C1-C10 alkyl and the heterocycle substituted by C1-C10 alkoxy; and R2 is H or CH2R1. According to the method, geranylamine, nitroguanidine and formaldehyde are mixed with an organic solvent to obtain a substituted triazine compound based on ring closure reaction, and then the triazine compound is mixed with aromatic heterocyclic methylene chloride or aromatic heterocyclic methylene bromine, acid-binding agent and organic solvent of different molar ratios to obtain the compound shown by the formula I based on condensation reaction. The compound shown by the formula I shows good chemical killing activity to aphids, and has good application value in aphid control.
Description
Technical field
The present invention relates to class novel heterocyclic pesticidal and an application thereof, relate in particular to a class and contain fragrant heterocycle triazines (instead)-β-farnesene analogue and the application on anti-eliminating aphis thereof.
Background technology
The aphid alarm pheromones is a kind of semiochemicals of aphid self secretion, to other individual alarm response that produces of the same race, it is fled the scene rapidly, thereby stop the infringement to crop.The seventies in last century, Bowers etc. discover that the main component of this liquid is (instead)-β-farnesene ((E)-β-farnesene is called for short EBF).Discovery EBF such as Francis are main or unique compositions of 16 kinds of aphid alarm pheromoneses.Except the activity of reporting to the police, EBF also has other multi-biological activity, the function that for example some insect is had similar neotonin III has the function of alatae and wingless aphid ratio among the regulation and control aphid offspring, when high dosage uses aphid is had obvious toxic action etc.Therefore, utilize this biological characteristics of natural EBF to carry out control of aphids, it is few to have a consumption, and specificity is strong, to advantages such as non-target organism and environmental safeties, thereby causes plant protection expert and agricultural producer's favor.But owing to have a plurality of pairs of keys in its structure of EBF, cause its volatile, easy oxidation, poor stability, limited it and be applied to the field control of aphids, therefore, need transform the structure of EBF.
Chinese scholars is from reducing degree of unsaturation and introducing aspect such as heteroatoms and start with molecule, it structural modification and transformation have been carried out, obtained having EBF analogue (Bowers W.S.et al.J.Insect Physiol.1977,23 (6): 697-701 that certain biological activity has better stability concurrently; Dawson G.W.et al.J.Chem.Eco., 1982,8 (11): 1377～1387; Briggs et al.Pesticide Science, 1986,17 (4): 441-448; Li Zhengming etc., chemical journal, 1987,45 (11): 1124-1128; Zhang Zhongning etc., insect journal, 1988,31 (4): 435-438).In recent years, in (instead)-β-farnesene structure, introduce nitrogen heterocyclic ring, as imidazolidine, oxadiazine ring, pyrazoles ring and other nitrogen heterocyclic rings etc., the synthetic part of compounds that obtains has better inhibited activity to aphid, for further development of new aphicide has been established good basis.(Yang Xin's tinkling of pieces of jade etc., SCI, 2004,25 (9): 1657-1661; Organic chemistry, 2008,28 (4): 617-621; Chinese invention patent: CN200310113701.8, CN200410098491.4, CN200710121334.4).
In recent years, have a lot of about compound in triazine class at the report aspect the insecticidal activity (Sun C.W.et al.J.Agric.Food Chem.2010,58:3415 – 3421; Bioorg.Med.Chem.Lett.2010,20:3301 – 3305; Eur.J.Med.Chem.2011,46:11-20; J.Agric.Food Chem.2011,59:4828 – 4835), triazine ring is considered to an effective insecticidal active group.
The present invention is by the thinking of active substructure splicing, the triazines active group that will have insecticidal activity is incorporated in (instead)-β-farnesene, conjugated double bond in alternative (instead)-β-farnesene structure is to improve its stability, invent a class and contained fragrant heterocycle triazines (instead)-β-farnesene analogue, the compound of inventing has tangible killing effect to the Agricultural pests aphid, can be used as aphicide and uses in agricultural.
Summary of the invention
The purpose of this invention is to provide a class and contain fragrant heterocycle triazines EBF analogue and the application on anti-eliminating aphis thereof.
A class provided by the present invention contains fragrant heterocycle triazines EBF analogue, is the described compound of formula I.
R wherein
1Be pyridine, thiazole, phenyl, pyrazoles, imidazoles, oxazole, isoxazole, quinoline, thiophene, furans, tetrahydrofuran (THF); Or the above-mentioned heterocycle that replaces of halogen, C1～C10 alkyl, C1～C10 alkoxyl group; R
2Be H or benzyl, methylene radical pyridine, methylene radical thiazole, methylene radical pyrazoles, methylene radical imidazoles, Ya Jia Ji oxazole, methylene radical isoxazole, methylene radical quinoline, methylene radical thiophene, methylene radical furans, methylene radical tetrahydrofuran (THF); Or by the above-mentioned methylene radical heterocycle of halogen, C1～C10 alkyl, C1～C10 alkoxyl group replacement.
Formula I compound can be prepared according to the method shown in the following reaction formula a:
Spiceleaf amine (raw material 1) and nitroguanidine and formaldehyde reaction are obtained 5-((E)-3,7-dimethyl-2, the 6-octadienyl)-1,3,5-Hexahydrotriazine-2-N-nitro-imine (intermediate 2), in the presence of acid binding agent and organic solvent, fragrant heterocycle METHYLENE CHLORIDE or the fragrant heterocycle methylene radical bromine with different mol ratio carries out condensation reaction again, product separates through silica gel column chromatography, obtains the target compound shown in the formula I.
Reaction formula a:
Described acid binding agent is organic bases or mineral alkali, is preferably one or more arbitrary combination in piperidines, sodium hydroxide, salt of wormwood, pyridine, triethylamine, 4-Dimethylamino pyridine, yellow soda ash, sodium methylate and the sodium hydride etc.
Described organic solvent comprises aliphatics, alicyclic or aromatic hydrocarbon or its halogenated product: such as, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin etc.; Ethers: as ether, diisopropyl ether, tetrahydrofuran (THF),, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycol dimethyl ether or ethylene glycol diethyl ether etc.; Ketone: as acetone, butanone or mibk etc.; Nitrile: as acetonitrile, propionitrile or butyronitrile etc.; Amides: as N, dinethylformamide, N,N-dimethylacetamide, N-methyl-formylaniline, N-Methyl pyrrolidone or HMPA etc.; Ester class: as methyl acetate or ethyl acetate etc.; Sulfoxide class: as dimethyl sulfoxide (DMSO); Alcohols: as methyl alcohol, ethanol, just-or Virahol etc. in one or more arbitrary combination.Described organic solvent is preferably benzene, acetonitrile, sherwood oil and N, one or more arbitrary combination in the dinethylformamide.
Described temperature of reaction is-10～100 ℃, and preferable reaction temperature is 30-80 ℃.
In the described method, also comprise reaction product is carried out column chromatography purification.
The anti-medicine that eliminates aphis that with the The compounds of this invention is activeconstituents also belongs to protection scope of the present invention.
Contain the preparation method of fragrant heterocycle triazines EBF analogue shown in the preparation formula I provided by the invention, simple to operate, with low cost.
Compound of the present invention the experiment proved that having tangible chemistry kills the aphid activity, and aphid is had direct chemical prevention effect, can be prepared as corresponding control of aphids agent.
Substantial characteristics of the present invention can be embodied from following embodiment, but it should not to be considered as be that the present invention is imposed any restrictions.
Embodiment
The present invention can be described further with following examples, but the present invention is not limited in these embodiment, and the method among the following embodiment if no special instructions, is ordinary method.
Embodiment 1:1-(6-chloro-3-picolyl)-5-((E)-3,7-dimethyl-2,6-octadienyl)-1,3, the preparation of 5-Hexahydrotriazine-2-N-nitro-imine (numbering 1)
Step 1:5-((E)-3,7-dimethyl-2,6-octadienyl)-1,3, the preparation of 5-Hexahydrotriazine-2-N-nitro-imine (intermediate 2)
In the 100ml there-necked flask, add 3.00g spiceleaf amine, 2.00g nitroguanidine and 20mL ethanol drip 1.58g formaldehyde solution, and 40 ℃ were reacted 3 hours.Filter filter cake ethanol rinse, dry white solid 5-((E)-3,7-dimethyl-2,6-octadienyl)-1,3,5-Hexahydrotriazine-2-N-nitro-imine (intermediate 2) 3g, the yield 54% of getting.
Step 2:1-(6-chloro-3-picolyl)-5-((E)-3,7-dimethyl-2,6-octadienyl)-1,3, the preparation of 5-Hexahydrotriazine-2-N-nitro-imine (numbering 1)
In the 100ml there-necked flask, add 0.5g2-chloro-5-chlorine methylene radical pyridine, 0.64g salt of wormwood, 0.86g5-((E)-3,7-dimethyl-2,6-octadienyl)-1,3,5-Hexahydrotriazine-2-N-nitro-imine and 20mL acetonitrile, back flow reaction 4 hours.Filter, solvent is sloughed in decompression, (elutriant is ethyl acetate: methylene dichloride V:V=1: 5) in the silica gel column chromatography separation, get white solid 1-(6-chloro-3-picolyl)-5-((E)-3,7-dimethyl-2, the 6-octadienyl)-1,3,5-Hexahydrotriazine-2-N-nitro-imine 0.78g(numbering 1), yield 64%.
1H?NMR：1.470(s,3H,CH
3),1.563(s,3H,CH
3),1.630(s,3H,CH
3),1.919-2.024(m,4H,),3.143(d,
3J
HH=6.6Hz,2H,CH
2),4.319(s,2H,CH
2),4.356(s,2H,CH
2),4.519(s,2H,CH
2),5.036-5.060(m,2H),7.525(d,J
HH=8.1Hz,1H),7.841-7.877(m,1H),8.392(d,J
HH=2.4Hz,1H),9.437(s,1H)。
Be respectively 2～8 target compound with the legal system call number.
Embodiment 2:1,3-two (6-chloro-3-picolyl)-5-((E)-3,7-dimethyl-2,6-octadienyl)-1,3, the preparation of 5-Hexahydrotriazine-2-N-nitro-imine (numbering 9)
In the 100ml there-necked flask, add 1g2-chloro-5-bromine methylene radical pyridine, 0.64g triethylamine, 0.86g5-((E)-3,7-dimethyl-2,6-octadienyl)-1,3,5-Hexahydrotriazine-2-N-nitro-imine (intermediate 2) and 20mL benzene, back flow reaction 4 hours.Filter, solvent is sloughed in decompression, (elutriant is ethyl acetate: methylene dichloride V:V=1: 1) in the silica gel column chromatography separation, get white solid 1,3-two (6-chloro-3-picolyl)-5-((E)-3,7-dimethyl-2, the 6-octadienyl)-1,3,5-Hexahydrotriazine-2-N-nitro-imine (numbering 9) 0.93g, yield 57%.
1H?NMR：1.535(s,3H,CH
3),1.597(s,3H,CH
3),1.666(s,3H,CH
3),1.956-2.032(m,4H,),3.141(d,
3J
HH=6.6Hz,2H,CH
2),4.270(s,4H,CH
2),4.606(s,4H,CH
2),4.914-4.969(m,1H),4.997-5.037(m,1H),7.389(d,J
HH=8.1Hz,2H),7.794-7.829(m,2H),8.324(d,J
HH=2.4Hz,2H)。
Be respectively 10～16 target compound with the legal system call number.
Below table 1 listed structure and the basic physicochemical data of target compound, they all are according to being similar to the prepared in various methods shown in the previous embodiment.
The materialization data of table 1 target compound (formula I)
| Numbering | R 1 | R 2 | Outward appearance | Fusing point (℃) | Yield (%) |
| 1 | The 2-Cl-pyridine | H | White solid | 102-104 | 64 |
| 2 | The 2-Cl-thiazole | H | White solid | 136-137 | 71 |
| 3 | The 2-F-pyridine | H | White solid | 92-94 | 59 |
| 4 | The 2-Br-pyridine | H | White solid | 95-96 | 62 |
| 5 | The 2-Br-thiazole | H | White solid | 115-116 | 61 |
| 6 | The 4-Cl-phenyl | H | White solid | 114-116 | 70 |
| 7 | 4-CF 3-phenyl | H | White solid | 104-106 | 68 |
| 8 | 4-CH 3-phenyl | H | White solid | 73-74 | 66 |
| 9 | The 2-Cl-pyridine | 2-Cl-pyridine-5-methyl | White solid | 117-118 | 57 |
| 10 | The 2-Cl-thiazole | 2-Cl-thiazole-5-methyl | Yellow oil | -- | 62 |
| 11 | The 2-F-pyridine | 2-F-pyridine-5-methyl | White solid | 84-86 | 60 |
| 12 | The 2-Br-pyridine | 2-Br-pyridine-5-methyl | White solid | 114-115 | 63 |
| 13 | The 2-Br-thiazole | 2-Br-thiazole-5-methyl | Yellow oil | -- | 61 |
| 14 | The 4-Cl-phenyl | The 4-Cl-benzyl | White solid | 104-106 | 65 |
| 15 | 4-CF 3-phenyl | 4-CF 3-benzyl | Yellow oil | -- | 67 |
| 16 | 4-CH 3-phenyl | 4-CH 3-benzyl | White solid | 94-96 | 63 |
Embodiment 4: The compounds of this invention is to the insecticidal activity of aphid
Target compound is taken by weighing the 50mg compound sample with ten thousand/balance in the 20ml weighing bottle, import the mensuration liquid that 10 mL volumetric flasks are made into 5000mg/L.Get 1ml acetone with the 1-5ml liquid-transfering gun again and add weighing bottle, add the aqueous solution that 9ml contains 0.1% triton x-100, abundant mixing gets the mensuration liquid of 500mg/L.Soybean leaves with the not contacted any medicament of indoor culture and insect, get the blade that is fit to size with the punch tool of diameter 15mm, immersed respectively in the good soup of dilution 15 seconds, taking-up is dried, put into living drafting board, leaf back up, the bottom adds 1% agar and preserves moisture, 20 of soybean aphids are inserted in every hole, and each repeats 3 times.Check result after 48 hours.Dead judging criterion is: touch polypide, the individuality of can not normally creeping is considered as death.
The calculation correction mortality ratio, formula is as follows:
Corrected mortality (%)=(sample mortality ratio-blank mortality ratio)/(1-blank mortality ratio) * 100% kills the aphid active testing and the results are shown in Table 2
Table 2 formula I target compound is to the insecticidal activity (concentration 500mg/L) of bean aphid
| Numbering | Corrected mortality (%) | Numbering | Corrected mortality (%) |
| 1 | 97.44 | 9 | 84.24 |
| 2 | 87.76 | 10 | 100.00 |
| 3 | 98.17 | 11 | 96.83 |
| 4 | 100.00 | 12 | 91.30 |
| 5 | 93.85 | 13 | 97.62 |
| 6 | 36.50 | 14 | 85.60 |
| 7 | 87.13 | 15 | 75.48 |
| 8 | 44.34 | 16 | 80.82 |
The result shows that compound of the present invention has the activity of killing to aphid, and wherein compound 1,3,4,5,10,11,12 and 13 under the dosage of 500mg/L to the inhibition mortality ratio of aphid all more than 90%, have the value of carrying out further application and development as the control of aphids agent.
Claims (8)
1. a class contains fragrant heterocycle triazines (instead)-β-farnesene analogue, it is characterized in that it is that general formula is the compound of formula I:
R wherein
1Be pyridine, thiazole, phenyl, pyrazoles, imidazoles, oxazole, isoxazole, quinoline, thiophene, furans, tetrahydrofuran (THF); Or by the above-mentioned heterocycle of halogen, C1～C10 alkyl, C1～C10 alkoxyl group replacement;
R
2Be H or benzyl, methylene radical pyridine, methylene radical thiazole, methylene radical pyrazoles, methylene radical imidazoles, Ya Jia Ji oxazole, methylene radical isoxazole, methylene radical quinoline, methylene radical thiophene, methylene radical furans, methylene radical tetrahydrofuran (THF); Or by the above-mentioned methylene radical heterocycle of halogen, C1～C10 alkyl, C1～C10 alkoxyl group replacement.
2. fragrant heterocycle triazines (instead)-β-farnesene analogue that contains according to claim 1 is characterized in that described R
1Preferred F, Cl, Br, CH
3, CF
3The pyridine, thiazole, the phenyl that replace.
3. fragrant heterocycle triazines (instead)-β-farnesene analogue that contains according to claim 1 is characterized in that described R
2Preferred H, and F, Cl, Br, CH
3, CF
3The benzyl, methylene radical pyridine, the methylene radical thiazole that replace.
4. the preparation method of fragrant heterocycle triazines according to claim 1 (instead)-β-farnesene analogue, it is characterized in that may further comprise the steps: spiceleaf amine, nitroguanidine, formaldehyde are mixed with organic solvent, the triaizine compounds that ring closure reaction obtains replacing, mix with fragrant heterocycle METHYLENE CHLORIDE or fragrant heterocycle methylene radical bromine, acid binding agent and the organic solvent of different mol ratio again, carry out condensation reaction, product separates through silica gel column chromatography, obtains the compound shown in the formula I.
5. according to the described preparation method who contains fragrant heterocycle triazines (instead)-β-farnesene analogue of claim 4, it is characterized in that, described organic solvent comprises aliphatics, alicyclic or aromatic hydrocarbon or its halogenated product: such as, benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, hexane, hexanaphthene, methylene dichloride, chloroform, tetracol phenixin etc.; Ethers: as ether, diisopropyl ether, tetrahydrofuran (THF),, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, glycol dimethyl ether or ethylene glycol diethyl ether etc.; Ketone: as acetone, butanone or mibk etc.; Nitrile: as acetonitrile, propionitrile or butyronitrile etc.; Amides: as N, dinethylformamide, N,N-dimethylacetamide, N-methyl-formylaniline, N-Methyl pyrrolidone or HMPA etc.; Ester class: as methyl acetate or ethyl acetate etc.; Sulfoxide class: as dimethyl sulfoxide (DMSO); Alcohols: as methyl alcohol, ethanol, just-or Virahol etc. in one or more arbitrary combination.Described organic solvent is preferably benzene, acetonitrile, sherwood oil and N, one or more arbitrary combination in the dinethylformamide.
6. according to the described preparation method who contains fragrant heterocycle triazines (instead)-β-farnesene analogue of claim 4, it is characterized in that, described acid binding agent is organic bases or mineral alkali, is preferably one or more arbitrary combination in piperidines, sodium hydroxide, salt of wormwood, pyridine, triethylamine, 4-Dimethylamino pyridine, yellow soda ash, sodium methylate and the sodium hydride etc.
7. according to the described preparation method who contains fragrant heterocycle triazines (instead)-β-farnesene analogue of claim 4, it is characterized in that described temperature of reaction is-10～100 ℃, preferable reaction temperature is 30-80 ℃.
8. fragrant heterocycle triazines (instead)-β-farnesene analogue that contains according to claim 1 can be used for preventing and treating crop and fruits and vegetables insect in agricultural, is preferred for anti-eliminating aphis.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271346A (en) * | 1997-08-20 | 2000-10-25 | 诺瓦提斯克 | Method for producing substituted 2-nitroguanidine derivative |
| CN1544421A (en) * | 2003-11-13 | 2004-11-10 | 中国农业大学 | Aphid alarm pheromone E-beta-Farmesene nitrogenous analog and its preparation method |
| CN101130525A (en) * | 2007-09-04 | 2008-02-27 | 中国农业大学 | [inverse]-beta- farnesene analogue, preparing method and application of the same |
-
2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1271346A (en) * | 1997-08-20 | 2000-10-25 | 诺瓦提斯克 | Method for producing substituted 2-nitroguanidine derivative |
| CN1544421A (en) * | 2003-11-13 | 2004-11-10 | 中国农业大学 | Aphid alarm pheromone E-beta-Farmesene nitrogenous analog and its preparation method |
| CN101130525A (en) * | 2007-09-04 | 2008-02-27 | 中国农业大学 | [inverse]-beta- farnesene analogue, preparing method and application of the same |
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Application publication date: 20130821 |