CN106243084B - A kind of Pyridylpyrrole quinoline compound and preparation method and application containing trifluoromethyl - Google Patents
A kind of Pyridylpyrrole quinoline compound and preparation method and application containing trifluoromethyl Download PDFInfo
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- CN106243084B CN106243084B CN201610622540.2A CN201610622540A CN106243084B CN 106243084 B CN106243084 B CN 106243084B CN 201610622540 A CN201610622540 A CN 201610622540A CN 106243084 B CN106243084 B CN 106243084B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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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
Abstract
The present invention relates to agricultural insecticide technical field more particularly to a kind of Pyridylpyrrole quinoline compounds containing trifluoromethyl for field of pesticides, have the following structure:Wherein, R1For H, halogen, C1‑7Alkyl, cyano, one of trifluoromethyl, R2For phenyl, substituted-phenyl, C1‑8One of alkyl；Through detecting, compound of the present invention has good control efficiency to diamondback moth and aphid, especially works as R1For 4- tert-butyl, R2When for phenyl, there is good control efficiency to cotten aphid, work as R1For 5-F, R2For phenyl or R1For 5-CF3, R2When for phenyl, there is 100% inhibiting rate to diamondback moth.
Description
Technical field
The present invention relates to agricultural insecticide technical field more particularly to a kind of Pyridylpyrrole quinoline chemical combination containing trifluoromethyl
Object and preparation method and application.
Background technique
The natural products of many azoles and dependency structure is present in plant, animal and microbial metabolic products
In, and show extensive bioactivity.These natural products include the chemical combination of desinsection, sterilization and plant growth regulating activity
Object, also including (Pesticide Science journal, 2002,4 (2): 1-13) such as insect attractant, repellant and anti-feedant.CRC Handbook
Of Natural Pesticides has commented the natural products of the insecticidal activity of many pyrroles and dependency structure.(CRC
Handbook of Natural Pesticides,VolⅢ:Insect Growth Regulators[M].Boca Raton,
Florida:CRC Press,Inc.,1987)
Many insects can generate various defensive alkaloids, wherein being also no lack of the chemical combination of pyrroles and its similar structures
Object.A large number of studies show that this Alkaloid is derived mainly from the arthropods such as ant, ladybug, spider and centipede.This kind of pyrroles's biology
Alkali has fully demonstrated its bio-diversity, has killing or repellent action to the various insects including aphid and mite class.
Later period eighties cyanamide company achieves important breakthrough in terms of the research of insecticidal activity azoles, and
Open report (Amer Chem Soc, 1992.395-404.) has been made to chlorfenapyr in the Britain crop protection meeting of nineteen ninety,
Hereafter, the said firm has carried out always lasting further investigation and other pesticide companies with regard to the synthesis of this kind of azoles
The research to such compound is added, has delivered some patents, it was found that many new high-activity compounds.
Trifluoromethyl is the essential group of numerous medicine and pesticide molecule, its introducing can significantly change molecule
(Nature, the 2011,473,470-477 such as polarity, lipophilicity and metabolic stability；Organic chemistry, 2012,32,815~
824)。
The extensive and excellent bioactivity and trifluoromethyl having in view of azoles is in medicine and pesticide
Important application, explore the azoles containing trifluoromethyl preparation method and product application field have it is important
Meaning.
Summary of the invention
The first purpose of the invention is to provide a kind of Pyridylpyrrole quinoline compound containing trifluoromethyl, compound tool
Just like flowering structure:
Wherein, R1For H, halogen, C1-7Alkyl, one of cyano or trifluoromethyl；R2For phenyl, substituted-phenyl or C1-8
One of alkyl.
Preferably, R1For 4 on pyridine ring or 5 bit substituents.
Preferably, R2For phenyl, C1-7One of alkyl or halogen atom substituted-phenyl, constructed from normal heptyl.
Most preferably, compound of the present invention has the following structure:
A second object of the present invention is to provide the preparation method of any one of the above compound, reaction process are as follows:
Reaction step are as follows:
(1) compound 1 and the process Michael addition reaction of compound 2 obtain compound 3；
(2) generation of compound 3 nitro-reduction reaction, intramolecular nucleophilic addition, dehydration obtain compound 4.
Wherein, the concrete operations of step (1) are as follows: work of the compound 1 and 2 in double oxazoline chiral ligands and nickel compound containing
Under, in -50 DEG C~50 DEG C reactions to get compound 3.
Preferably, double oxazoline chiral ligands areThe nickel compound containing is Ni
(ClO4)2；
It is further preferred that double oxazoline chiral ligands and Ni (ClO4)2Molar ratio be (1.1-1.2): 1.
Preferably, the reaction temperature is 0-10 DEG C.
Preferably, the reaction of step (1) carries out in a solvent, and the solvent is selected from methanol, ethyl alcohol, isopropanol, tetrahydro furan
It one of mutters, further preferably isopropanol.
Preferably, the molar ratio of compound 1 and compound 2 is 1:(1-2).
Preferably, the mole dosage of the nickel compound containing accounts for the 1-20% of compound 1, further preferably 10%.
Preferably, the reaction of step (1) carries out under inert gas protection.
Wherein, the concrete operations of step (2) are as follows: compound 3 metal and acid catalysis under, in 60-70 DEG C reaction to get
Compound 4.
Preferably, the metal is selected from one of iron, zinc, aluminium.
Preferably, the acid is selected from hydrochloric acid or acetic acid.
Most preferably, step reaction carries out the present invention under iron and acetic acid catalysis.
Preferably, the molar ratio of compound 2 and metal and acid is 1:(40-50): (10-20) is further preferably 1:
45:16。
Preferably, step (2) carries out in a solvent, and the solvent is the mixed solvent of alcohol-containing, further preferably methanol
The mixed solvent formed with methylene chloride, ethyl alcohol and tetrahydrofuran, methanol and tetrahydrofuran, isopropanol and tetrahydrofuran, wherein
The volume ratio of pure and mild another kind solvent is 1:(1-3).The most preferred reaction dissolvent of the present invention is the methanol and four of volume ratio 1:2
Hydrogen furans mixed solvent.
Preparation method of the present invention further includes being post-processed the system after the reaction of each step to extract target product
The step of, filtering can be used in the post-processing, extracts, distillation, column chromatography for separation, crystallization, the skill commonly used in the art such as recrystallization
Art means.
Wherein, compound 1 and compound 2 of the present invention are known compound, commercially available acquisition, or according to existing
The means that technology discloses are prepared.Specifically:
Compound 1 can refer to Tetrahedron, 2008,64,3794. and J.Org.Chem. 2006,71 (3), 1009-
The method preparation of 1014. reports, the specific method is as follows:
Wherein, replacing R group in above-mentioned reaction is R of the present invention1Corresponding compound 1 can be obtained in corresponding group.
Compound 2 can refer to chemical reagent, 2006,28 (7), 444-445. and J.Am.Chem.Soc., and 2010,403,
The method preparation of 398-404. report, the specific method is as follows:
Similarly, replacing phenyl in above-mentioned reaction is R of the present invention2Corresponding compound 2 can be obtained in corresponding group.
The present invention obtains target compound, total recovery 65-85%, product optical purity 90-99% through two-step method, and is somebody's turn to do
Method also has reaction condition mild, and catalyst is simple, easy to operate advantage.
Third object of the present invention is to provide more than one to state the insecticide that any compound is active constituent.
The insecticide can be made into dosage form commonly used in the art, such as aqua, suspending agent, pulvis, dispersing agent, finish.
As known to those skilled in the art, auxiliary material or auxiliary agent, the choosing of the auxiliary material or auxiliary agent can be also contained in the insecticide
Select can be according to specific dosage form depending on, the present invention does not do particular determination.
Fourth object of the present invention is to provide any one of the above compound or any one insecticide in prevention and treatment pickles
Application in moth or aphid.
It has been investigated that lethality and avermectin or imidacloprid of the compound of the present invention to diamondback moth and aphid
Quite, there is good insecticidal effect.
Wherein, as the R in general formula compound1For 4- tert-butyl, R2For phenyl, i.e. specific structure is's
Compound has optimal control efficiency to aphid.
As the R in general formula compound1For 5-F, R2For phenyl or R1For 5-CF3, R2For phenyl, i.e., following structural compounds
There is 100% inhibiting rate to diamondback moth.
Reagent or raw material of the present invention are known product.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined with each other each preferably to get the present invention
Embodiment.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
The preparation of 1 compound 4a of embodiment
Double oxazoline ligand 92mg (0.275 mmol), Ni (ClO are added into dry 100mL round-bottomed flask4)2
(0.254mmol), be added isopropanol 10mL, stir 30 min at room temperature, add 2mL isopropanol dissolution 1a (303mg,
2.5mmol), after stirring 30min at 0 DEG C, the 2a (814mg, 3.75mmol) of 3mL isopropanol dissolution is added.After sample-adding, 0
It is reacted for 24 hours at DEG C.To end of reaction, reaction mixture directly passes through silica gel column chromatography separating-purifying (acetic acid second after depressurizing precipitation
Ester: petroleum ether=1:10, volume ratio), obtain white solid 3a, 0.8g (yield 94%).
In 50mL flask, 3a (0.68g, 2mmol) is dissolved in MeOH/AcOH solvent, add iron powder (5g, 45eq) and
AcOH (1.8mL, 16eq) installs reflux unit, and 65 DEG C of heating 3h are filtered after completion of the reaction, and ethyl acetate washs filter residue, filter
Organic phase is successively with the Na of saturation in liquid2CO3Solution, strong brine washing, anhydrous sodium sulfate is dry, and crude product is used after removing solvent
Mixed solvent recrystallization purification (ethyl alcohol: ethyl acetate=5:1, volume ratio), obtains white solid 4a 0.48g (yield 83%).
m.p.:44-45℃；(c=0.5, CH2Cl2)；98%ee；HPLC measures [Daicel
Chiralcel AD-H column, n-hexane/isopropanol (volume ratio)=90:10, flow velocity 0.80mL/min, Detection wavelength 254nm]
；1H NMR (300MHz, CDCl3): δ 8.67 (d, J=4.8Hz, 1H), 8.16 (d, J=7.9Hz, 1H), 7.77 (td, J=
7.7,1.7Hz, 1H), 7.48 7.30 (m, 6H), 5.01 (dd, J=15.0,3.0Hz, 1H), 4.59 (d, J=75.0, Hz,
1H), 4.09 (dd, J=15.0,3.0Hz, 1H), 3.70 (d, J=21.0Hz, 1H)；13C NMR (75MHz,CDCl3)δ
(172.72,152.00,148.93,138.10,136.28,128.37,127.90,127.62 q, J=281.3Hz),
(124.93,121.67,68.80,55.07 q, J=25.1Hz), 43.31；ESI-HRMS calculated value C16H14F3N2 ([M+H]
+): 291.1104, measured value 291.1104.
The preparation method of 2 compound 4d of embodiment
Double oxazoline ligand 92mg (0.275 mmol), Ni (ClO are added into dry 100mL round-bottomed flask4)2
(65mg, 0.254mmol) is added isopropanol 10mL, is stirred at room temperature 30 minutes under nitrogen protection, add the dissolution of 2mL isopropanol
1b (337.5mg, 2.5 mmol), stir 30 minutes at 0 DEG C, be added the dissolution of 3mL isopropanol 2a (814mg,
3.75mmol).After sample-adding, reacted for 24 hours at 0 DEG C.Reaction mixture directly passes through silica gel column chromatography after solvent is removed under reduced pressure
Separating-purifying (ethyl acetate: petroleum ether=1:4, volume ratio), obtains white solid 3ba, 836.7mg (yield 95%).
In 50mL round-bottomed flask, 3ba (710mg, 2mmol) is dissolved in MeOH/AcOH solvent, add iron powder (5g,
45eq), AcOH (1.8mL, 160eq) installs condensing unit, and 65 DEG C of heating 3h are filtered after completion of the reaction, ethyl acetate washing filter
Slag, organic phase is successively with the Na of saturation in filtrate2CO3Solution, strong brine washing, anhydrous sodium sulfate is dry, slightly produces after removing solvent
Product recrystallize purification (ethyl alcohol: ethyl acetate=3:1) with mixed solvent, obtain white crystal 4d 0.5g (yield 77%).
m.p.:83-84℃ ；[α]=- 34.6 (c=0.50, CH2Cl2)；92%ee, HPLC detect [Daicel
Chiralcel AD-H column, n-hexane/isopropanol=90:10, flow velocity 1.0mL/min, wavelength 254nm]；1H NMR
(300MHz, CDCl3) δ 8.47 (s, 1H), 8.04 (d, J=7.8Hz, 1H), 7.57 (m, 1H), 7.44 7.30 (m, 5H),
4.95 (d, J=16.9Hz, 1H), 4.55 (d, J=17.1Hz, 1H), 4.07 (d, J=18.4Hz, 1H), 3.66 (d, J=
18.5 Hz,1H),2.38(s,3H).13C NMR(75MHz,CDCl3)δ172.61,149.48, 149.31,138.16,
(136.83,135.04,128.35,127.86,127.65 q, J=282.2 Hz), 121.22,68.69,53.19,55.05 (q,
), J=25.1Hz 43.30,43.28,18.29.ESI-HRMS calculated value C17H15F3N2 ([M+H]+): 305.1260, measurement
Value 305.1259.
The preparation method of 3 compound 4h of embodiment
Double oxazoline ligand 92mg (0.275 mmol), Ni (ClO are added into dry 100mL round-bottomed flask4)2
(0.254mmol), be added isopropanol 10mL, stir 30 min at room temperature, add 2mL isopropanol dissolution 1a (303mg,
2.5mmol), after stirring 30min at 0 DEG C, the 2b (896mg, 3.75mmol) of 3mL isopropanol dissolution is added.After sample-adding, 0
It is reacted for 24 hours at DEG C.To end of reaction, reaction mixture directly passes through silica gel column chromatography separating-purifying (acetic acid second after depressurizing precipitation
Ester: petroleum ether=1:10, volume ratio), obtain white solid 3bh 0.81g (yield 90%).
In 50mL flask, 3bh (0.624g, 2mmol) is dissolved in MeOH/AcOH solvent, add iron powder (5g, 45eq) and
AcOH (1.8mL, 16eq) installs reflux unit, and 65 DEG C of heating 3h are filtered after completion of the reaction, and ethyl acetate washs filter residue, filter
Organic phase is successively with the Na of saturation in liquid2CO3Solution, strong brine washing, anhydrous sodium sulfate is dry, and crude product is used after removing solvent
Mixed solvent recrystallization purification (ethyl alcohol: ethyl acetate=5:1, volume ratio), obtains yellow oil 4h 0.50g (yield
80%).
(c=0.69, CH2Cl2)；1H NMR(300MHz,CDCl3) δ 8.61 (d, J=4.3Hz,
1H), 8.09 (d, J=7.8Hz, 1H), 7.73 (t, J=7.1Hz, 1H), 7.36 7.28 (m, 1H), 4.34 (d, J=
17.5Hz, 1H), 4.02 (d, J=17.5 Hz, 1H), 3.42 (d, J=18.6Hz, 1H), 3.18 (d, J=18.4Hz, 1H),
1.76 1.55 (m, 2H), 1.25 (s, 10H), 0.82 (d, J=6.7Hz, 3H)13C NMR(75MHz, CDCl3)δ172.39,
152.09,148.84,136.07,128.77 (q, J=280.6 Hz), 125.13,124.68,122.00,121.57,
(104.59,67.02,49.85 q, J=24.6 Hz), 41.40,33.82,31.47,29.80,28.75,28.66,23.38,
22.29,13.70. ESI-HRMS calculated value C17H23F3N2 ([M+H]+): 313.1886, measured value 313.1882.
Using method similar to Example 1, R in simple replacement compound 1 and compound 21And R2Group, can obtain
To the compound of structure as shown in table 1 below:
Table 1: the specific structure and fusing point and yield of compound
| Compound | R1 | R2 | Fusing point (DEG C) | Yield (%) |
| 4a, FBW-1 | H | C6H5 | 44-45 | 83 |
| 4b, FBW-2 | 5-F | C6H5 | 82-84 | 76 |
| 4c, FBW-3 | 5-Br | C6H5 | 65-67 | 68 |
| 4d, FBW-4 | 5-Me | C6H5 | 84-86 | 77 |
| 4e, FBW-5 | 5-CF3 | C6H5 | 44-46 | 71 |
| 4f, FBW-6 | 4-CN | C6H5 | 94-96 | 81 |
| 4g, FBW-7 | 4-tBu | C6H5 | 98-100 | 76 |
| 4h, FBW-8 | H | C7H15 | yellow oil | 80 |
| 4i, FBW-9 | 5-Me | C7H15 | yellow oil | 77 |
| 4j, FBW-10 | 5-Br | C7H15 | yellow oil | 80 |
| 4k, FBW-11 | 5-CF3 | C7H15 | yellow oil | 75 |
Effect experimental examples
It is tested with infusion process into the insecticidal activity for having carried out cotten aphid and diamondback moth to FBW series compound.With avermectin
It is control with imidacloprid (medicine inspecting institute of the Ministry of Agriculture provides).
Diamondback moth (Plutella xylostella Linnaeus) picks up from Beijing's vegetable fields, carries out laboratory experiment use
The raising of brassicaceous vegetable blade, condition are room temperature (27 ± 1) DEG C, and humidity 80%, intensity of illumination 2000lux, light application time is every
Its 12h.Indoors under rearing conditions, agent activity sieve is carried out with worm age, weight and the almost consistent 2 age primary larva of physiological status
Choosing test.
Cotten aphid (Aphis gossypii Glover), picks up from Haidian District, Beijing City field, is transferred to the cotton plant of chamber planting
Upper captive breeding carries out agent activity screening test after mass propagation.
At 200mg/L, compound is to diamondback moth and cotten aphid insecticidal activity, measurement result such as the following table 2 institute in test table 1
Show:
Table 2: measurement result of the present invention to diamondback moth and cotten aphid insecticidal activity
Wherein, comparison medicament imidacloprid and avermectin experimental concentration are 200mg/L, and CK is blank control.
To cotten aphid insecticidal activity assay, the experimental results showed that, under the concentration of 200mg/L, all test compounds are to cotten aphid
There is a degree of inhibitory activity, correct the death rate between 10%-77%, FBW-7 compound is best to the activity of cotten aphid
It is 77%.In the inhibitory activity test to diamondback moth, FBW-2 and FBW-5 compound shows 100% lethality, has
Develop into the potentiality of agricultural insecticide.
Although above having used general explanation, specific embodiment and test, the present invention is made to retouch in detail
It states, but on the basis of the present invention, it can be made some modifications or improvements, this is apparent to those skilled in the art
's.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed
Range.
Claims (7)
1. application of the Pyridylpyrrole quinoline compound as active constituent on insecticide containing trifluoromethyl；
The Pyridylpyrrole quinoline compound containing trifluoromethyl has the following structure:
Wherein, R1For H, halogen, C1-7Alkyl, one of cyano or trifluoromethyl；R2For phenyl, substituted-phenyl or C1-8Alkyl
One of.
2. application according to claim 1, it is characterised in that: R1For 4 on pyridine ring or 5 bit substituents, R2For phenyl,
C1-7One of alkyl or halogen atom substituted-phenyl, constructed from normal heptyl.
3. application according to claim 2, it is characterised in that: the compound has the following structure:
4. application according to claim 1-3, it is characterised in that: the application in prevention and treatment diamondback moth or aphid.
5. application according to claim 4, it is characterised in that: the aphid is cotten aphid.
6. application according to claim 4, it is characterised in that: the compound has the following structure:
7. application according to claim 5, it is characterised in that: the compound has the following structure:
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