CN101427678B - Plant source bactericide and artificial synthesis thereof - Google Patents
Plant source bactericide and artificial synthesis thereof Download PDFInfo
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- CN101427678B CN101427678B CN 200810055369 CN200810055369A CN101427678B CN 101427678 B CN101427678 B CN 101427678B CN 200810055369 CN200810055369 CN 200810055369 CN 200810055369 A CN200810055369 A CN 200810055369A CN 101427678 B CN101427678 B CN 101427678B
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- phthalic acid
- ester
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- monooctyl ester
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Abstract
The invention relates to the preparation domain of plant source pesticide, especially a plant source bactericide and artificial synthesis method thereof, in order to solve that the essential oil in marigold is used as plant source bactericide and applied in plant pathogen. The bactericide is penta-octyl-ester phthalate and the formula is, firstly the phthalic acid reacts with pantanol at alkaline condition to generate monopentyl-ester soduim-salt phthalate, and then the monopentyl-ester soduim-salt phthalate reacts with octano to generate penta-octyl-ester phthalate solution; the water phase is removed and the organic phase collects volatile component by the distillation way to obtain penta-octyl-ester phthalate. The plant source bactericide has features of simple operation method, mild reaction condition, high yield, suitable for large-scale industrialization production, more important, the plant source bactericide is applied for the plant source pesticide, with obvious killing function to the plant pathogen such as watermelon, pumpkin, pepper wilt, tomato leaf mold, gray mold, with high inhibition rate and provides new path of the development of Chinese plant source pesticide.
Description
Technical field
The present invention relates to the botanical pesticide preparation field, be specially a kind of botanical fungicide and artificial synthesis thereof.
Background technology
The application of agricultural chemicals is the important means that guarantees to improve grain yield; Synthetic organic pesticide; Especially chemical insecticide; When bringing higher yield of crops and good harvest, also owing to irrational use has produced " 3R " (Residue, Resistance, Resurgence, promptly residual, resistance, rampant again) problem of not allowing suddenly to be looked.Compare with chemical pesticide, the advantage of botanical pesticide is: to the low toxicity of people, animal and beneficial organism, product and environment are all shown as low residue and be prone to degraded, the influence to biological and environment in effective prevention and elimination of disease and pests drops to minimally; Botanical pesticide belongs to stomach poison function to the mode of action of controlling object more, and most contactless toxicity escape injury the beneficial insect beneficial bird of non-planting property of food; Effective constituent in the botanical pesticide is as the secondary metabolites of plant; Wherein a part is the ego defense chemical substance of plant; Harmful organism is had concurrently the effect of desinsection, sterilization and coordinate plant growth; With chemical pesticide different mechanism of action is arranged, so help overcoming the focus that the resistance botanical pesticide of harmful organism becomes people's research.It is the desirable agricultural chemicals of development Organic farming, promotion agricultural sustainable development.
At present, the development and use of botanical pesticide can be divided into two aspects: the one, and direct utilization is after promptly the active substance in the plant slightly being extracted. directly be processed into available preparation.The 2nd, indirect utilization is promptly studied the relation between structure, mechanism of action, structure and the activity of active substance, and then the synthetic screening of manual simulation, therefrom development of new botanical pesticide preparation.Advantages such as two kinds of approach are compared, and direct utilization has convenient for production, and technology is simple still seriously receive the restriction of raw material, and effect also will receive the restriction of product.But indirect utilization has suitability for industrialized production, can methods such as proportioning synthetic through homologue and different products enlarge its effect greatly, and owing to be the biogenic material, can be the same with crude substance pollution-free, noresidue; But there is technological line complicated, requires level high, the restriction of the big grade of research difficulty.Indirect utilization is the emphasis of current external botanical pesticide research and development.It also is the direction of plant-based pesticides researchdevelopment.
Botanical pesticide is divided into plant insecticide and botanical fungicide.The research and the application of the two plant insecticide of comparing are used considerably beyond botanical fungicide.The 39 kind of plant source pesticide overwhelming majority of registration are sterilants now.Because exploitation causes domestic research and development now mainly to rest in the direct development and use of botanical pesticide in the technology of aspects such as research and development and the restriction of fund indirectly, seldom gets into the indirect development phase.The sterilant that has only two kinds of these aspects now, the i.e. sterilant 402 (with the garlicin molecular structure is template, the synthetic analogue ethylicin of deriving) and the green base of a fruit (chemical structure with biologically active substance B in the ginkgo is that the template synthetic is intended the ginkgo sterilant).
Flower of Aztec Marigold (Marigold; Formal name used at school Tagetes erecta), is commonly called as tagetes erecta, is the composite family plants of tagetes species.Bloom summer and autumn, and it is yellow or orange that flower is, and is easy to cultivation.Kind surplus plants of tagetes species has 30, middle part, main product America and south, wherein many is ornamental plants.For the exploitation of Flower of Aztec Marigold, mainly be to be used to extract food dye now, some investigators have also carried out the research of its extract to the killing action of insect (like the mosquitos and flies class) and mite class (tetranychus viennensis).Some research also shows, also contains the plant sterilization material in the Flower of Aztec Marigold, is the essential oil class, but up to the present, also not seeing has the report of Flower of Aztec Marigold as botanical fungicide.
Watermelon blight is dead arm, wilt etc. again, is worldwide watermelon producing region disease, and each watermelon producing region of China all has blight to take place; Its sickness rate is generally about 15%; Reach more than 80% when serious, even the withered total crop failure in full field, production causes serious economy loss to watermelon.Except that watermelon, it is melon also to contaminate cucumber, muskmelon and muskmelon etc.Along with the rapid expansion of the melon cultivated area of peasant, this disease has become one of severe diseases of the melon production of influence.
Summary of the invention
The present invention does not see now some derived essential oil of utilizing in the Flower of Aztec Marigold is arranged as botanical fungicide and the problem that is applied in the report in the germ such as watermelon blight in order to solve, and a kind of botanical fungicide and artificial synthesis thereof are provided.
The present invention adopts following technical scheme to realize: a kind of botanical fungicide, this sterilant are phthalic acid penta monooctyl ester, and its molecular formula is C
21H
32O
4, structural formula is following:
Through detecting, the molecular weight of phthalic acid penta monooctyl ester is 348; Physico-chemical property is following: outward appearance: yellow translucent oily liquids; Special aroma is arranged; Content is 99.2%; Boiling point is 320～322 ℃; Solvability: water not fully is soluble in organic solvent; Stability: normal temperature is stable down; Volatility: volatility slightly.
Botanical fungicide-phthalic acid penta monooctyl ester according to the invention; Be according to research to the various extracting solutions of Flower of Aztec Marigold; Learn that the main bacteriocidal substance of Flower of Aztec Marigold is the essential oil class; Through essential oil class substance germicide composition is used the GC/MS structural analysis, learn that one of composition that content wherein is higher is phthalic acid penta monooctyl ester.This material can directly extract from Flower of Aztec Marigold, but the content that from natural product, extracts usually is few, is unfavorable for research or application, so the invention provides a kind of method of synthetic, concrete steps are following:
(1) preparation of phthalic acid list pentyl ester sodium salt
With 1: 1.00～1.20 mixed in molar ratio, under 95～115 ℃ temperature, react 1.8h～2h by phthalic acid and Pentyl alcohol, be cooled to 50～60 ℃ then; Slowly drip NaOH solution; Regulate pH value to 7.0～8.5, promptly get the aqueous solution of phthalic acid list pentyl ester sodium salt, reaction formula is following:
(2) phthalic acid penta monooctyl ester is synthetic
In the aqueous solution of above-mentioned phthalic acid list pentyl ester sodium salt, add n-Octanol; Add catalyzer then; The mol ratio of above-mentioned phthalic acid, n-Octanol and catalyzer is 1: 1.00～1.20: 0.01, under 100～115 ℃ temperature, reacts 3～4h, is cooled to 50～60 ℃ then; The reaction solution that obtains is changed in the separating funnel, discard water layer, behind the organic layer water repetitive scrubbing; Through vapor distillation, underpressure distillation, collect 320～322 ℃ cut, get yellow translucent oily liquids; Special aroma is arranged; Be phthalic acid penta monooctyl ester, said vapor distillation, underpressure distillation are techniques well known, and reaction formula is following:
Described catalyzer is any one in tetrabutylammonium chloride or Tributylamine or the bromination dodecyl dimethyl benzylamine, and the above-mentioned reaction conditions that the present invention adopts is best, and not only speed of response is fast, and efficiency of pcr product is high.
In order to prove that further the final product that compound method according to the invention obtains is phthalic acid penta monooctyl ester, carried out following detection especially,
(1), instrument: U.S. Agilent HP6890N gas chromatograph
(2), testing conditions: flame ionization ditector (FID), post are Dexsil-300GC fusion fused-silica capillary column (30m * 0.25mm * 0.25um); N
2Be carrier gas; 250 ℃ of temperature of vaporization chamber; 200 ℃ of sensing chamber's temperature; No split stream sampling device, 6890N/GC chemical work chamber.Column and programmed temperature: 80 ℃ keep 2min, with the temperature rise rate of 4 ℃/min, are warming up to 180 ℃, and the temperature rise rate with 10 ℃/min is warming up to 250 ℃ of maintenances 15 minutes again; Nebulizer gas pressure is 1.0kgcm
-2, splitting ratio 30: 1, tail blows 0.4kgcm
-2, sample size 0.15ul, sensitivity 10
-10Adapted CDMC-IB chromatographic data treatment system is carried out data processing.
(3), standard specimen: from Flower of Aztec Marigold, purify and phthalic acid penta monooctyl ester through detecting.
(4), sample: technology synthetic product according to the invention.
(5), operation: make the one matter gc of standard specimen and sintetics respectively, like Fig. 1, shown in 2, the gc of compound sample is as shown in Figure 3 after the two being mixed again;
(6), interpretation of result: through the collection of illustrative plates three's of standard specimen (phthalic acid penta monooctyl ester of natural purification) collection of illustrative plates and sintetics collection of illustrative plates of the present invention and standard specimen+sintetics mixture comparative analysis; No matter be the RT of one matter; Still the two is mixed later RT; The RT of standard specimen and sintetics is all very approaching, explains that synthetic product of the present invention is phthalic acid penta monooctyl ester.
In order further to prove the effect of resulting phthalic acid penta monooctyl ester of the present invention, carried out following test especially as botanical fungicide:
A, phthalic acid penta monooctyl ester are to the germicidal action of withered germ of water-melon
Phthalic acid penta monooctyl ester is made into the medicament substratum of concentration 1.5,1.0,0.8,0.5,0.1,0.05,0.01 μ g/ml respectively; According to the normal experiment method; Carry out bacteriostatic experiment respectively, watermelon blight mycelia growing state behind observation 24h, 36h, 48h, the 72h writes down the hyphal diameter under each time; Obtain the MV of three colony diameters in each same petridish of the moment; The result is as shown in the table, accompanying drawing 4,5,6,7 shows respectively in addition be the phthalic acid penta monooctyl ester solution of different concns (1 μ g/ml, 0.5 μ g/ml, 0.05 μ g/ml, 0.01 μ g/ml) to the contrast photo of withered germ of water-melon in the germicidal action of 48h, wherein left photo is contrast CK (promptly not adding phthalic acid penta monooctyl ester medicament substratum); Right photograph is a sample
Annotate: the hyphal diameter in the table under each time is the MV of three colony diameters in each same petridish of the moment.
Can find out that by above table phthalic acid penta monooctyl ester is comparatively obvious to the inhibition effect of watermelon blight mycelia growth, is that withered germ of water-melon is suppressed fully under the 1.5ug/ml in concentration; In concentration is under the 0.1ug/ml, and the inhibiting rate of 24h can reach 100%, and the inhibiting rate of 72h can reach 41.7%; In concentration is under the 0.05ug/ml, and mycelia has just just begun growth behind the 24h; In concentration is under the 0.01ug/ml, and the inhibiting rate of 24h can reach 58.3%, and the inhibiting rate of 48h can reach 50.2%, and the inhibiting rate behind 72h can reach 34.6%.Can find out by accompanying drawing simultaneously, under identical action time,, higher at phthalic acid penta monooctyl ester to the inhibiting rate of withered germ of water-melon along with the increase of its concentration.
The fungicidal spectrum research of B, phthalic acid penta monooctyl ester
Warp confirms that it is a wide-spectrum bactericide, all has killing action to following germ: withered germ of water-melon, pumpkin wilt to the research of the fungicidal spectrum of phthalic acid penta monooctyl ester; The capsicum wilt, phytophthora capsici, leaf muld of tomato bacterium, botrytis cinerea; Pears mould germ, Glorosprium musarum Cookeet Mass, sclerotium blight of sunflower bacterium; Summer squash white powder germ, gibberella saubinetii, plan dish crinosity born of the same parents bacterium etc.As shown in Figure 8, be contrast photo to phytophthora capsici, as shown in Figure 9, be contrast photo to fusarium graminearum, left photo is contrast, and the right side is sample.
The present invention at first adopts phthalic acid and Pentyl alcohol reacting by heating under alkaline condition, obtains phthalic acid list pentyl ester sodium salt, and then under the effect of catalyzer, reacts generation phthalic acid penta monooctyl ester solution with n-Octanol; Remove water; According to the boiling point of penta monooctyl ester of phthalic acid in the organic phase, collect fugitive constituent through the distillation mode, obtain the finished product phthalic acid penta monooctyl ester; This compound method is simple to operate, reaction conditions is gentle, reaction result is more single; Productive rate is high, can reach more than 90% suitability for mass industrialized production; Since be the biogenic material, the same with crude substance pollution-free, noresidue; The more important thing is to be applied to botanical pesticide to have tangible killing action to the germ of plants such as blights such as watermelon, pumpkin, capsicum, leaf muld of tomato, gray mold, inhibiting rate is higher, for the development of plant-based pesticides provides new approach.
Description of drawings
Fig. 1 is the gas chromatogram of phthalic acid penta monooctyl ester of standard specimen
Fig. 2 is the gas chromatogram of synthetic phthalic acid penta monooctyl ester of the present invention
Fig. 3 is the gas chromatogram of the compound sample of standard specimen and sintetics of the present invention
Fig. 4 is that 1 μ g/ml phthalic acid, penta monooctyl ester solution is to the contrast photo of withered germ of water-melon in the germicidal action of 48h for concentration
Fig. 5 is that 0.5 μ g/ml phthalic acid, penta monooctyl ester solution is to the contrast photo of withered germ of water-melon in the germicidal action of 48h for concentration
Fig. 6 is that 0.05 μ g/ml phthalic acid, penta monooctyl ester solution is to the contrast photo of withered germ of water-melon in the germicidal action of 48h for concentration
Fig. 7 is that 0.01 μ g/ml phthalic acid, penta monooctyl ester solution is to the contrast photo of withered germ of water-melon in the germicidal action of 48h for concentration
Fig. 8 is the contrast photo of phthalic acid penta monooctyl ester solution to phytophthora capsici
Fig. 9 is the contrast photo of phthalic acid penta monooctyl ester solution to fusarium graminearum
Embodiment
Embodiment 1:
A kind of botanical fungicide, this sterilant are phthalic acid penta monooctyl ester, and its molecular formula is C
21H
32O
4, structural formula is following:
Embodiment 2:
A kind of botanical fungicide, this sterilant are phthalic acid penta monooctyl ester, and its molecular formula is C
21H
32O
4, structural formula is following:
Embodiment 3:
A kind of botanical fungicide, this sterilant are phthalic acid penta monooctyl ester, and its molecular formula is C
21H
32O
4, structural formula is following:
Embodiment 4:
A kind of botanical fungicide, this sterilant are phthalic acid penta monooctyl ester, and its molecular formula is C
21H
32O
4, structural formula is following:
Claims (3)
1. phthalic acid penta monooctyl ester is as the application of botanical fungicide, and the molecular formula of phthalic acid penta monooctyl ester is C
21H
32O
4, structural formula is following:
2. prepare the artificial synthesis of botanical fungicide phthalic acid penta monooctyl ester as claimed in claim 1, it is characterized in that may further comprise the steps:
(1) preparation of phthalic acid list pentyl ester sodium salt
With 1: 1.00～1.20 mixed in molar ratio, under 95～115 ℃ temperature, react 1.8h～2h by phthalic acid and Pentyl alcohol, be cooled to 50～60 ℃ then; Slowly drip NaOH solution; Regulate pH value to 7.0～8.5, promptly get the aqueous solution of phthalic acid list pentyl ester sodium salt, reaction formula is following:
(2) phthalic acid penta monooctyl ester is synthetic
In the aqueous solution of above-mentioned phthalic acid list pentyl ester sodium salt, add n-Octanol; Add catalyzer then; The mol ratio of above-mentioned phthalic acid, n-Octanol and catalyzer is 1: 1.00～1.20: 0.01, under 100～115 ℃ temperature, reacts 3～4h, is cooled to 50～60 ℃ then; The reaction solution that obtains is changed in the separating funnel, discard water layer, behind the organic layer water repetitive scrubbing; Through vapor distillation, underpressure distillation, collect 320～322 ℃ cut, get yellow translucent oily liquids; Special aroma is arranged, be phthalic acid penta monooctyl ester, reaction formula is following:
3. the artificial synthesis of botanical fungicide according to claim 2 is characterized in that described catalyzer is tetrabutylammonium chloride or Tributylamine or bromination dodecyl dimethyl benzylamine.
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| CN 200810055369 CN101427678B (en) | 2008-07-05 | 2008-07-05 | Plant source bactericide and artificial synthesis thereof |
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| CN 200810055369 CN101427678B (en) | 2008-07-05 | 2008-07-05 | Plant source bactericide and artificial synthesis thereof |
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| CN101427678B true CN101427678B (en) | 2012-05-09 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105284896A (en) * | 2015-10-10 | 2016-02-03 | 平顶山市玉龙山生态农业科技发展有限公司 | Bactericide for preventing and treating watermelon fusarium wilt diseases and preparation method of bactericide |
| CN105340964A (en) * | 2015-10-10 | 2016-02-24 | 平顶山市玉龙山生态农业科技发展有限公司 | Bactericide used for preventing and treating downy mildew of cucumber and preparation method thereof |
| CN106342805B (en) * | 2016-08-31 | 2018-08-14 | 山东农业大学 | Application of the diisooctyl phthalate on prevention Fusarium solani and bacterial wilt |
| CN114213236A (en) * | 2021-11-30 | 2022-03-22 | 上海寻科生物医药科技有限公司 | Synthesis of Yeast dehydrogenase inhibitors |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086132A (en) * | 1964-01-25 | 1967-10-04 | Basf Ag | Continuous production of o-phthalic esters |
| CN1122326A (en) * | 1992-03-27 | 1996-05-15 | 赫彻斯特股份公司 | Decyl alcohol mixtures, phthalic esters obtainable therefrom and their use as plasticizers |
| CN1143627A (en) * | 1995-08-22 | 1997-02-26 | 烟台市福山科源化工厂 | Process for producing butyl benzyl phthalate |
-
2008
- 2008-07-05 CN CN 200810055369 patent/CN101427678B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1086132A (en) * | 1964-01-25 | 1967-10-04 | Basf Ag | Continuous production of o-phthalic esters |
| CN1122326A (en) * | 1992-03-27 | 1996-05-15 | 赫彻斯特股份公司 | Decyl alcohol mixtures, phthalic esters obtainable therefrom and their use as plasticizers |
| CN1143627A (en) * | 1995-08-22 | 1997-02-26 | 烟台市福山科源化工厂 | Process for producing butyl benzyl phthalate |
Non-Patent Citations (4)
| Title |
|---|
| Asilbekova, D. T. ET AL..Lipids of the fruit of Acanthopanax sessiliflorus.《Chemistry of natural compounds》.1985,第21卷(第6期),719-724. * |
| 张慧玲等.强酸树脂催化合成邻苯二甲酸混合酯增塑剂.《广西大学学报(自然科学版)》.1996,第21卷(第4期),377-382. * |
| 李永才等.苹果梨果皮中预存抗菌物质的提取、分离与鉴定.《食品工业科技》.2006,第27卷(第2期),49-52. * |
| 王千秋.邻苯二甲酸810酯的合成.《精细与专用化学品》.2004,第12卷(第7期),7-8. * |
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