CN103819343B - The preparation method of the fluoro-6-nitrophenols of compound 2-allyl group-4-and agricultural biological activity - Google Patents
The preparation method of the fluoro-6-nitrophenols of compound 2-allyl group-4-and agricultural biological activity Download PDFInfo
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- CN103819343B CN103819343B CN201410052200.1A CN201410052200A CN103819343B CN 103819343 B CN103819343 B CN 103819343B CN 201410052200 A CN201410052200 A CN 201410052200A CN 103819343 B CN103819343 B CN 103819343B
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Abstract
Disclose a kind of compound 2-allyl group-4-fluoro-6-nitrophenols preparation method and purposes.Dissolved by 2-allyl group-4-fluorophenol with chloroform, temperature control, at 5 ~ 10 DEG C, drips the nitration mixture be made up of in the ratio of 1:4-9 sulfonitric.Drip and finish, stirring reaction for some time.Steam solvent, residue with ethyl acetate extracts, and organic phase obtains target compound through washing, evaporation desolventizing.It is active that this compound has wide spectrum, efficiently agricultural bactericidal, has good restraining effect to weeds.
Description
Technical field
The present invention is preparation method and the agricultural biological activity of the fluoro-6-nitrophenols of compound 2-allyl group-4-, is specifically related to organic compound, organic synthesis and agriculture sterilization and weeding field.
Background technology
Phenolic compound is the important secondary metabolites that the plant such as ginkgo, onion, celastrus angulatus, Herba Scutellariae Barbatae, rheum officinale produces, and often demonstrates the biological activitys such as antibacterial, desinsection, weeding, for botanical pesticide exploitation provides lead compound.Because fluorine atom electronegativity is large, radius is little, the C-F key bond energy formed can be much bigger than c h bond, thus make organofluorine compound have good stability.After importing fluoro-containing group at active compound, because fluorine-containing substituent electronic effect, blocking effect, pseudo-plan effect, osmotic effect synergy create complicated physiologically active.The initiative of Drugs Containing Fluorine has become the important directions of new pharmaceutical, novel pesticide exploitation.By synthesis for many years and Activity Screening Test, we find that 2-allyl group-4-fluoro-6-nitrophenols has good sterilization and weeding activity.
Patent documentation WO2003048159A1 describes the synthetic method of the fluoro-6-nitrophenols of 2-allyl group-4-: with 2-nitro-4-fluorophenol and bromopropylene for raw material, preparation 2-nitro-4-fluorophenyl allyl ether, then resets the fluoro-6-nitrophenols of preparation 2-allyl group-4-through the Claisen of microwave-assisted.The etherification procedure of the method controls strict, and rearrangement process needs microwave-assisted.We find with the 2-allyl group-4-fluorophenol being easy to prepare for raw material, take chloroform as solvent, and with the nitration mixture of sulfonitric composition by a certain percentage for nitrating agent prepares target compound by nitration reaction, be easy to control, convenient post-treatment, yield is high.
Biological activity test shows, the fluoro-6-nitrophenols of target compound 2-allyl group-4-has outstanding fungicidal activity than 4-fluorophenol, 2-allyl group-4-fluorophenol, 2-nitro-4-fluorophenol etc.
Summary of the invention
The object of this invention is to provide a kind of preparation method and the purposes of compound 2-allyl group-4-fluoro-6-nitrophenols.
The solution of the present invention is as follows:
The bromo-4-of 2-fluoro-6-nitrophenols can be prepared by following route:
Key step is as follows:
Dissolved by 2-allyl group-4-fluorophenol with chloroform, temperature control, at 5 ~ 10 DEG C, drips the nitration mixture be made up of in the ratio of 1:4-9 sulfonitric.Drip and finish, stirring reaction for some time.Steam solvent, residue with ethyl acetate extracts, and organic phase obtains target compound through washing, evaporation desolventizing.
Synthetic method of the present invention has following features: reactions steps is few, starting material are cheap and easy to get, simple to operate, process stabilizing, yield are high, be conducive to suitability for industrialized production.
Compound of the present invention has wide spectrum, efficiently fungicidal activity, withers, the phytopathogen such as wheat total eclipse has higher restraining effect to apple decay, oranges and tangerines anthrax, Chinese cabbage grey mold, cotton; Good restraining effect is had to weeds such as barnyard grasses.
Following examples are used for further illustrating the present invention, but are not limited to the present invention.
Synthesis specific embodiment
The synthesis of the fluoro-6-nitrophenols of target compound 2-allyl group-4-
In reaction flask, add 2-allyl group-4-fluorophenol 0.025 mole, chloroform 20ml, stirring and dissolving, temperature control, at 5 ~ 10 DEG C, dropwise drips by the sulfonitric nitration mixture 0.0325 mole that forms of 1:5.5 in molar ratio, drips and finish, stirring reaction 2 hours.Reaction is finished, and decompression steams solvent.Residue with ethyl acetate extraction (3 × 20ml), organic phase washed with water, anhydrous sodium sulfate drying, filter, evaporation of filtrate obtains crude product, through silica gel column chromatography, obtains faint yellow waxy crystalline (heating is easily melted, in oily), yield 68%.
The sign of the fluoro-6-nitrophenols of target compound 2-allyl group-4-
Mass spectroscopy shows, the molecular weight of gained compound is 197.2, conforms to theoretical value.
Nuclear magnetic data: (
1h, 500MHz, CDCl
3)
δ：10.91(1H，s，ArOH)，7.69～7.72(1H，dd，Ar-H)，7.26～7.29(1H，dd，Ar-H)，5.93～6.00(1H，m，-CH=C)，5.15～5.21(2H，m，-C=CH
2)，3.49～3.51(2H,d,-CH
2-)。
Infrared data:
ν/cm
-1: 3232 (ν
s:-OH), 3098 (ν
as:C=C), 2925 (ν
as:-CH2), 2853 (ν
s:-CH2), 1092 (ν
as:C-F), 1602 and 1456 (phenyl ring skeletal vibrations), 868 (1,2,3,5-tetra-substituted benzene ring C-H out-of-plane deformation vibrations).
Agricultural chemicals (fungicidal activity) typical case measure:
Getting appropriate certain density 2-allyl group-4-fluoro-6-nitrophenols liquid, to be placed in 100mL temperature be about 50 DEG C PDA sterilising mediums, shake up, pouring diameter into is in the sterilizing culture dish of 60mm, after cooled and solidified, move the bacterium cake that length is consistent, diameter is 5mm of delivering a child respectively, to add the sterilising medium of equivalent coordinative solvent as blank, often 3 repetitions are established in process.After putting into 25 DEG C of constant incubators cultivation one timings, adopt right-angled intersection method to measure colony diameter, with pure increment for benchmark bacteriostasis rate, ask for 50 1.143851e-144ffective concentration EC
50.As, take-all former bacterium EC withered to apple decay, oranges and tangerines anthrax, Chinese cabbage grey mold, cotton
50be respectively 14.5,24.0,10.9,17.3,11.7mg/L.The fungicidal activity of target compound is apparently higher than 4-fluorophenol, 2-allyl group-4-fluorophenol, 2-nitro-4-fluorophenol compound.As to gaeumannomyces graminis, respectively with 5,10,20,40, the dosage of 80mg/L tests, and obtains the EC of 2-allyl group-4-fluorophenol, 2-nitro-4-fluorophenol
50be respectively 70.80,20.30mg/L; And 4-fluorophenol effect is the poorest, when 80mg/L, inhibiting rate is also only 26.2%, can not calculate EC
50.
Agricultural chemicals (weeding activity) typical case measure:
By test plant seed after 0.2% chlorine bleach liquor soaks 15min, with tap water juxtaposition stream underwater soaking about 4h for several times, then with distilled water wash several, evenly be placed on the thieving paper in square plate with cover, drip distilled water not floating to seed, shading is placed in complete intelligent growth cabinet germinates, and when roots of plants reaches about 2mm, just can select and be used as planting experimentally bud.Transplanting kind of bud to preparing on the gel that active constituent content is 100mg/L with the acetone soln of the fluoro-6-nitrophenols of 2-allyl group-4-and 0.5% agar solution in advance, making blank with equivalent acetone, each process establish 3 parallel.Inoculate, put it into growth cabinet shading and cultivate.Growth cabinet is set to the automated cycle of 14h (25 DEG C), 10h (20 DEG C), and relative humidity is 60%.After contrast group leader is good, measure the length of test plant radicle and plumular axis respectively with electronics vernier callipers, with pure increment for benchmark inhibiting rate.As being respectively 100% and 77.2% to barnyard grass radicle and plumular axis inhibiting rate.
Claims (3)
1. the preparation method of the fluoro-6-nitrophenols of 2-allyl group-4-: add 2-allyl group-4-fluorophenol 0.025 mole, chloroform 20ml in reaction flask, stirring and dissolving, temperature control is at 5 ~ 10 DEG C, dropwise drip by the sulfonitric nitration mixture 0.0325 mole that forms of 1:5.5 in molar ratio, drip and finish, stirring reaction 2 hours; Reaction is finished, and decompression steams solvent; Resistates 3 × 20ml extraction into ethyl acetate, organic phase washed with water, anhydrous sodium sulfate drying, filter, evaporation of filtrate obtains crude product, through silica gel column chromatography, obtains product.
2. the fluoro-6-nitrophenols of compound 2-allyl group-4-according to claim 1 is in the application of controlling plant diseases.
3. the fluoro-6-nitrophenols of compound 2-allyl group-4-according to claim 1 is in the application of control plant crop smothering.
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| WO2002030924A1 (en) * | 2000-10-13 | 2002-04-18 | Astrazeneca Ab | Quinazoline derivatives with anti-tumour activity |
| WO2003048159A1 (en) * | 2001-12-05 | 2003-06-12 | Astrazeneca Ab | Quinoline derivatives |
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| WO2013088256A1 (en) * | 2011-12-12 | 2013-06-20 | Dr. Reddy's Laboratories Ltd. | Substituted pyrazolo[1,5-a] pyridine as tropomyosin receptor kinase (trk) inhibitors |
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Patent Citations (5)
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|---|---|---|---|---|
| WO2002030924A1 (en) * | 2000-10-13 | 2002-04-18 | Astrazeneca Ab | Quinazoline derivatives with anti-tumour activity |
| WO2003048159A1 (en) * | 2001-12-05 | 2003-06-12 | Astrazeneca Ab | Quinoline derivatives |
| WO2003047583A1 (en) * | 2001-12-05 | 2003-06-12 | Astrazeneca Ab | Pharmaceutical compositions comprising benzofuranyl substituted 3-cyanoquinoline derivatives and their use for the treatment of solid tumours |
| WO2013088256A1 (en) * | 2011-12-12 | 2013-06-20 | Dr. Reddy's Laboratories Ltd. | Substituted pyrazolo[1,5-a] pyridine as tropomyosin receptor kinase (trk) inhibitors |
| CN102617502A (en) * | 2012-03-19 | 2012-08-01 | 江苏先声药物研究有限公司 | Benzoxazole derivatives and application of benzoxazole derivatives to medicines |
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