CN1843114A - Pesticide uses of compound 4-hydroxy sesquiterpene propyl ester - Google Patents
Pesticide uses of compound 4-hydroxy sesquiterpene propyl ester Download PDFInfo
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Abstract
The invention provides an extract of radix euphorbiae ebracteolatae of daphnetoxin by skellysolve B and the usage of the further got active compound A and B in pesticide. The target insect is vegetable insect, and it is demonstrated by biological activity test that: when the extract is diluted for 30 times, the corrected mortality of insect is 100% in 72 hours; the activity of contact action of compound A: 1,5-Biphenyl-3-Hydroxy-1-Pentanone is 483.4 mg/l (LC50); and it is 530.3 mg/l (LC50) for compound B: 4-Hydroxy-Sesquiterpene- Propylene-Es ter. The invention lies foundation for producing new pollution-free pesticide with radix euphorbiae ebracteolatae.
Description
The application is that denomination of invention is
The preparation of insecticide active substance and purposes in the Chinese Stellera Root, application number is
200510021333.3, the applying date is
On July 27th, 2005The dividing an application of application for a patent for invention.
Technical field
The present invention relates to the purposes of a kind of Chinese Stellera Root active substance in agricultural chemicals, belong to pesticide field.
Background technology
Because the long-term unreasonable use of chemical pesticide, bring many drawbacks, as caused environmental pollution, to the direct murder by poisoning of non-target organism, insect easily develops immunity to drugs etc.Recent year, along with the development of the enforcement of IPM theory, the strategy of sustainable development and human raising to self health requirements, environment compatibility is good, the research and development of safety, low-residual, economic biopesticide are subject to people's attention day by day, is accepted by market just gradually.Plant pesticide is just becoming the research focus of initiative novel pesticide.
Chinese Stellera Root (StellerachanlaejastneL.), the red root of langdu, silk floss wipe out greatly, one perfume, red match end, gelsemium elegan.Mongolia's name: Da Lun-Tu Ru.Be Thymelaeceae stellera plant, the beginning is stated from Shennong's Herbal, and with the euphorbia plant euphorbia fischeriana, euphorbia ebiacteolata Hayata is with being used as medicine as the root of langdu, and its nature and flavor are bitter flat, poisonous, relieve oedema or abdominal distension through diuresis or purgation and eliminate the phlegm, the effect of broken long-pending desinsection.Its decocting liquid treatment cancer of the stomach of usefulness among the people, intestinal cancer, aqueous vapor swelling, scrofula, bone tuberculosis and pulmonary tuberculosis etc.In recent years, the root of langdu has become one of comparatively serious plant of Chinese meadow harm.It is reported that the root of the root of langdu can be used for making biopesticide-vegetable insecticide, this insecticide insect is had tags, stifling and stomach poison function.And it is fast to have drug effect, and the term of validity is long, high-efficiency low-toxicity, and noresidue, free from environmental pollution, do not destroy advantages such as the ecological balance, no pesticide resistance.Xie Qingke report root of langdu solution spray, can prevent and treat cabbage caterpillar, aphid, soybean pod borer, two-spotted spider mite, agrotis, loose high and steep moth, pine caterpillars, pine sawfoy etc., with root of langdu preparation also can kill mosquito, drive fly, the maggot of going out, bedbug, louse and flea all there are special efficacy, can be used to prevent and treat crops, fodder grass, fruit tree, vegetables and injurious forest-insect.
Stellera chamaejasme L extract is a lot of in the research of pesticide field, such as Zhang Guozhou etc., but mainly rests on ethanol extract to tagging of cabbage caterpillar etc., does not see the report that uses n-hexane extract at present, and report extract active component portion clear and definite.At present, mainly getting from Chinese Stellera Root is flavonoids and coumarin kind compound; Liu Gui virtue etc. is also told cupreol, Daucosterol compounds such as (Daucosterol) from the auspicious root of langdu in addition.[Feng Baomin, Pei Yuehu, Han Bing, " Chinese Stellera Root chemical constitution study ", Shenyang Pharmaceutical University's journal, 2000,17 (4), p258-259] three compounds identifying are disclosed, comprising compd A 1,5-diphenyl-3-hydroxyl-1-pentanone, but do not point out the purposes of this compound.
Summary of the invention
Technical program of the present invention lies in providing the purposes of a kind of Chinese Stellera Root n-hexane extract in insecticide pesticide.Contain among compd A, the B one or more in the described Chinese Stellera Root n-hexane extract.
Compd B 4-hydroxy sesquiterpene propyl ester
It is the agricultural chemicals of main active that the present invention also provides with Chinese Stellera Root n-hexane extract, compd A, compd B.Described agricultural chemicals can be to be that active component is prepared from by the Chinese Stellera Root n-hexane extract, and it contains n-hexane extract 2000～3000mg/L, or the compd A of 500～1000mg/L; Or the compd B of 1500～2000mg/L.
Wherein, described n-hexane extract is by the preparation of following method: with Chinese Stellera Root root powder with 7～15 times of amount soaked in absolute ethyl alcohol, extraction, concentrate, again with n-hexane extraction, concentrated n-hexane extract.
The preparation method of described compd A and/or B is as follows: wherein fixing is silica gel H mutually;
A, huge pillar rough segmentation
Fixing phase: silica gel H; 1), n-hexane-ethyl acetate-carrene (volume ratio is 1: 1: 1) flowing phase: (volume ratio is 20 ~ 1: with n-hexane-ethyl acetate; Post footpath: 12cm, conventional wet method dress post, the about 15cm of silica gel height, with the N-hexane extract in the flow process one is sample separation, each applied sample amount 25g, flow velocity 10ml/min, gradient elution, divide three sections collect big shell of column 1, section 2, section 3, each section is with the thin layer detection and carry out biological activity determination.Active strong part is further segmented as the next step initial sample.
B, center pillar segmentation
Fixing phase: silica gel H, post footpath 5cm, conventional wet method dress post, the high about 40cm of silicagel column, center pillar on the huge pillar rough segmentation sample segments 2 that activity is higher, sections 3 is gone up sample 5g at every turn; Flow velocity 2.5ml/min, 1), n-hexane-ethyl acetate-carrene (volume ratio is 1: 1: 1), carrene-ethyl acetate-methyl alcohol (volume ratio is 10: 10: 2) flowing phase: (volume ratio is 10～1: with n-hexane-ethyl acetate; Gradient elution, fraction collection merges R after thin-layer chromatography detects
fBe worth identical flow point, obtain three flow points, middle shell of column 1, section 2, section 3 are carried out biological activity determination, select the high flow point of biologically active, carry out next step column chromatography segmentation.
C, pillar segmentation
Fixing phase: silica gel H, post footpath 3cm, conventional wet method dress post, the high about 40cm of silicagel column, center pillar sample segments 2 upper props that activity is the highest are gone up sample 2g at every turn; Flowing phase: with n-hexane-ethyl acetate (volume ratio is 4: 1), carrene-ethyl acetate (volume ratio is 1: 1); Gradient elution merges after thin-layer chromatography detects, and is used for biological activity determination, and the biologically active that gets pillar section 2 is the highest.Still have 2 bands of a spectrum in section 2, changing the eluant, eluent condition can't separate, so adopt reversed phase column chromatography to carry out next step separation.
D, reverse phase silica gel post separate
Fixing phase: reverse phase silica gel, post footpath 2cm, conventional wet method dress post, the high about 30cm of silicagel column, purer sample pillar section 2 upper props that activity is the highest, 2g at every turn; Flowing phase: methanol-water-oxolane (volume ratio is (10～20): (2～5): (3～7)), methyl alcohol-oxolane (volume ratio is 1: 1); Gradient elution detects the back through anti-phase thin layer and merges identical flow point, concentrate single bands of a spectrum sample A and B, change solvent condition repeatedly and carry out thin layer and detect definite purity.
Among the preparation method of Chinese Stellera Root n-hexane extract provided by the invention, ethanol infiltration is strong, be easy to infiltrate plant tissue, active principle extracts fully, ethanol (especially hot ethanol) solubility property is good simultaneously, in addition absolute ethyl alcohol cheap in addition, be easy to reclaim, to outstanding advantages such as human toxicity are little, go up choosing when extracting on a large scale beyond doubt.Advantages such as the n-hexane extraction product of Chinese Stellera Root root still comprises more component, and the separation of the compound of such complexity is cumbersome, adopts the segmentation column chromatography to have the solvent of saving, silica gel, saving manpower, and separating effect is better.At first carry out the first branch of huge pillar and can carry out rude classification, remove some permanent absorption impurity, experiment shows that huge pillar just divides very good to rough segmentation extract subsection efect, one step can improve active ingredient purity more than 4 times, and the minimizing of sample volume simultaneously also helps being further purified of step down.Gradient elution is adopted in center pillar segmentation, adopts the gradient elution of pillar at last, and the separation of carrying out the reverse phase silica gel post obtains pure product compd A and B.
Imported cabbageworm Pieris rapae Linnaeus, English name: cabbage butterfly, popular name cabbage white butterfly, sulphur butterfly, larva another name cabbage caterpillar.Belonging to the Lepidoptera Sulfur butterfly, promptly is the larva of imported cabbageworm to the cabbage caterpillar of the bigger harm of agricultural components.Cabbage caterpillar not only causes breach and worm excrement to pollute when gnawing the blade of green vegetables, also propagates germs such as soft rot of Chinese cabbage, insect high-incidence season even the vegetables eat everything up only can be stayed petiole, has a strong impact on vegetables quality.To the control of this insect, mainly rely on chemical pesticide for a long time, not only killed and wounded a large amount of natural enemies, and cause the cabbage caterpillar pesticide resistance to strengthen,, form vicious circle to such an extent as to have to strengthen dosage and number of times, cause in the vegetables persticide residue big, influence vegetables quality, jeopardize health etc.
Evidence, when Chinese Stellera Root n-hexane extract provided by the invention diluted 30 times, in the 72h was 100% to the cabbage caterpillar corrected mortality, the lethal concentration of 50 (LC of contact toxicity
50) be 812.1mg/L; In test food refusal rate, concentration (AFC in the food refusal of N-hexane extract
50) be 4006mg/L, illustrate that the root of langdu has stronger poisoning and antifeedant activity to cabbage caterpillar.Obtained active ingredient, compd A through further separating: 1, (1,5-Diphenyl-3-Hydroxy-1-Pentanone), its contact toxicity to cabbage caterpillar is 483.4mg/L (LC to 5-diphenyl-3-hydroxyl-1-pentanone
50); And compd B: 4-hydroxy sesquiterpene propyl ester (4-Hydroxy-Sesquiterpene-Propylene-Es ter), its contact toxicity to cabbage caterpillar is 530.3mg/L (LC
50).
In a word, pesticide efficacy provided by the invention is fast, the term of validity is long, quality controllable, for agricultural provides a kind of high-efficiency low-toxicity, noresidue, new selection free from environmental pollution, can prevent and treat cabbage caterpillar, aphid, soybean pod borer, two-spotted spider mite, agrotis, loose high and steep moth, pine caterpillars, pine sawfoy etc., also can kill mosquito, drive fly, the maggot of going out, bedbug, louse and flea are also had special efficacy.
Description of drawings
Fig. 1 stellera chamaejasme L extract of the present invention prepares schematic diagram;
The separation and purification schematic diagram of Fig. 2 Chinese Stellera Root effective active composition;
Fig. 3 compd A
1The H nmr spectrum;
Fig. 4 compd B
1The H nmr spectrum.
Embodiment
The preparation of embodiment 1 stellera chamaejasme L extract and contact toxicity are measured
Chinese Stellera Root picks up from Ruoergai grassland, Sichuan Province, and the fresh Chinese Stellera Root root that collection is returned is cleaned and dried, and pulverizes with cracker, obtains fine hair shape root of langdu powder.
Take by weighing a certain amount of Chinese Stellera Root root dry powder, extraction concentrates after the soaked in absolute ethyl alcohol of 10 times of quality of adding, does fractional extraction with opposed polarity solvent n-hexane, chloroform, ethyl acetate, methyl alcohol respectively again, obtains the opposed polarity extract, repeat 3 times to extracting fully, merge identical extract.
According to the method that Zhang ZongBing introduces, adopt antifeedant activity and contact toxicity to measure virulence simultaneously: at first do not gather cabbage caterpillar in the vegetable plot of agricultural chemicals is used in the countryside, it is individual for the experiment use 3 ages to carefully choose the health that polypide is of moderate size.
With gained sample and dimethyl sulfoxide (DMSO), the missible oil ratio with 1: 1: 2 (mass ratio), with the fully emulsified mixing of ultrasonic, water dilution constant volume is as treatment fluid, and is standby.Contrast liquid is with distilled water: dimethyl sulfoxide (DMSO): the ratio preparation of missible oil=1: 1: 2 (mass ratio), water dilution constant volume is standby.
Test the antifeedant activity of extract: fresh cabbage leaves is broken into the leaf dish with circular card punch (diameter 2cm), treatment fluid and contrast liquid are pressed gradient dilution to cabbage caterpillar.Feed to cabbage caterpillar in the processed group leaf dish that treatment fluid handled, control group fed contrasts the leaf dish that liquid was handled.Select for use 3 age cabbage caterpillar, every group 20 cephalont repeated 3 times.Dish leaf and cabbage caterpillar are put into φ 15 culture dishes that are covered with filter paper, and the dependent insect cage that closes prevents that cabbage caterpillar from climbing mistake, puts room temperature (25 ℃), observes during respectively at 24h, 48h after handling and 72h, gets the food area with the graph paper record.
Test the contact toxicity of extract: adopt dip method, the examination worm is put in the treatment fluid and contrast liquid that is dipped in the filter screen by gradient dilution, take out behind the 3s, treat that polypide surface soup dries, and will try worm and be put in the dependent insect cage to cabbage caterpillar.The clean cabbage leaves of all feeding.Select 3 instars for use, hungry 6h, every group 20 cephalont repeated 3 times.Observe the record death condition respectively at handling back 24h, 48h and 72h.
Activity the results are shown in Table 1.And mensuration 24h food refusal rate.
The different SCEE extracts of table 1 are to the tagging of cabbage caterpillar, antifeedant activity
| Sample 24h absolute ethyl alcohol 75.2 57.8 43.7 25 | Concentration (mg/L) 48h 5 * 1,000 87.7 76.8 69 44.2 | Corrected mortality (%) 72h | Food refusal rate (%) 24h | ||
| 94.2 86.8 81.2 55.7 | 99.2 91.3 70.7 52 | The extract n-hexane | 2.5×1000 1.25×1000 6.25×100 11.11×l000 | ||
| 75 50 37.5 25 | 87.5 67.5 50 25 | 100 87.5 50 37.5 | 100 100 100 100 | The extract chloroform | 3.703×1000 1.234×1000 4.113×100 11.11×l000 |
| 6.5 0 0 0 | 7.5 2.5 0 0 | 18.8 6.3 0 0 | 80 50 33.3 10 | Extract ethyl acetate | 3.703×1000 1.234×1000 4.113×100 8.000×1000 |
| 12.5 10.3 0 0 | 25 21.3 12.5 6.8 | 30 25 18.8 12.5 | 50 37.5 25 12.5 | Extract methyl alcohol | 4.000×1000 2.000×1000 1.000×1000 7.711×1000 |
| 37.5 33.3 25 0 | 50 40 37.8 6.7 | 55.6 47.5 41.3 16.7 | 50 45 25 25 | Extract | 3.855×1000 1.928×1000 9.638×100 |
As can be seen from Table 1, the contact toxicity of N-hexane extract is the highest, the 72h lethal concentration of 50 (LC
50) be 812.1mg/L, the methanol extraction thing secondly: in test food refusal rate, the biologically active of N-hexane extract is the strongest, secondly is chloroform extract, is that methanol extraction thing, acetic acid ethyl ester extract weaken successively then.Therefore, next step is that starting point is passed through the purification on normal-phase silica gel column separating purification with the N-hexane extract.
The chromatography purifying of embodiment 2 Chinese Stellera Root deinsectization active substances
Make fixedly phase of adsorption chromatography with tlc silica gel GF254, bed board according to a conventional method on the automatic bed board instrument of thin layer.Thin plate size: 5 * 10 (cm), silica gel thickness: 0.25mm.The plank of completing is put into baking oven and is dried by the fire half an hour for 105 ℃, leaves in the drier stand-by after the cooling.With point sample capillary point sample, the mixed solvent of forming different proportion with the difference of n-hexane, chloroform, ethyl acetate, carrene, methyl alcohol equal solvent is a solvent exhibition layer respectively, exhibition layer back with 254nm ultra-violet analysis light irradiation and iodine powder steam, sulfuric acid-three kinds of methods of ethanol colour developing in conjunction with detecting bands of a spectrum.Select good separating effect, the solvent condition that does not trail is for the column chromatography reference.
The huge pillar rough segmentation
During huge pillar just divides, select n-hexane-ethyl acetate (volume ratio is 20: 1), adopt gradient elution, increase polarity gradually, to n-hexane-ethyl acetate-carrene (volume ratio is 1: 1: 1) as initial eluant, eluent.Each section wash-out flow point of collecting is after concentrating, and thin layer detects and biological activity determination.
The big column chromatography flow point of table 2 is to the tagging of cabbage caterpillar, antifeedant activity
| Flow point | Concentration (mg/l) | Corrected mortality (%) | Food refusal rate (%) | ||
| 24h | 48h | 72h | | ||
| Huge pillar | |||||
| 1 | 43.32×1000 10.83×1000 2.708×1000 6.769×100 | 62.5 18.8 12.5 0 | 68.8 43.8 12.5 12.5 | 75 50 18.8 12.5 | 50 20 11.1 9.1 |
| Huge | 48.55×1000 12.14×1000 3.034×1000 7.586×100 | 100 93.8 56.3 43.8 | 93.8 62.5 50 | 100 68.8 55 | 100 95 90 85 |
| Huge pillar 3 | 40.00×1000 10.00×1000 2.500×1000 6.250×100 | 100 90 56.7 27.3 | 95 75 45.5 | 100 80 54.6 | 100 95 80 50 |
The center pillar segmentation
Adopt n-hexane-ethyl acetate (volume ratio is 10: 1,4: 1,1: 1), n-hexane-ethyl acetate-carrene (volume ratio is 1: 1: 1), carrene-ethyl acetate-methyl alcohol (volume ratio is 10: 10: 2); Gradient elution, fraction collection is got 3 flow points, and each flow point detects and biological activity determination through thin layer; Section 1 contains 2 bands of a spectrum approximately, and section 2 contains 3 bands of a spectrum approximately, and section 3 contains 2 bands of a spectrum approximately.Section 1, section 2 have bands of a spectrum to intersect, and then both also have bands of a spectrum to intersect.
Active result such as table 3:
The column chromatography flow point is to the tagging of cabbage caterpillar, antifeedant activity in the table 3
| Flow point | Concentration (mg/l) 48h 5.684 * 1,000 20 13.3 10.1 0 | Corrected mortality (%) 72h | Food refusal rate (%) 24h | ||
| 26.7 20 13.3 0 | 20.7 11.1 6.7 3.3 | | 1.421×1000 3.553×100 8.881×10 5.951×1000 | ||
| 66.7 20 6.7 6.7 | 87.8 40 13.3 6.7 | 93.3 66.7 26.7 13.3 | 100 100 78.3 52.9 | Center pillar 3 | 1.488×1000 3.719×100 9.289×10 4.763×1000 |
| 50 30 6.7 0 | 60 37.5 13.3 0 | 70 45 18.8 0 | 100 90 60 50 | 1.191×1000 2.977×100 7.442×10 | |
The result shows that section 2 has biologically active preferably, proceeds little column separating purification.
The pillar segmentation
Adopt n-hexane-ethyl acetate (volume ratio is 4: 1), carrene-ethyl acetate (volume ratio is 1: 1), gradient elution obtains three flow points.Each flow point detects and biological activity determination through thin layer, and the result is as follows:
Table 4 pillar chromatography flow point is to the tagging of cabbage caterpillar, antifeedant activity
| Flow point | Concentration (mg/l) | Corrected mortality (%) | Food refusal rate (%) | ||
| 24h | 48h | | 24h | ||
| Pillar | |||||
| 1 | 4.173×1000 1.043×1000 2.608×100 8.694×10 | 50 20 0 0 | 60 40 10 0 | 70 50 10 0 | 100 95 90.5 73.9 |
| | 4.092×1000 1.023×1000 2.558×100 8.525×10 | 90 40 0 0 | 100 70 6.7 0 | 80 13.3 0 | 100 98 88.2 87.8 |
| Pillar 3 | 5.571×1000 1.393×1000 3.482×100 1.161×10 | 30 20 5 0 | 45 40 20 0 | 70 50 30 0 | 100 97 77.8 60 |
The reverse phase silica gel post separates
Adopt methanol-water-oxolane (volume ratio is 16: 4: 5), methyl alcohol-oxolane (volume ratio is 1: 1); Gradient elution, the reverse phase silica gel thin plate detects, and solvent is methanol-water-oxolane (volume ratio is 16: 4: 5), and testing result is as follows:
By the reverse phase silica gel post, from the section 2 of pillar, separate two the pure product of A, B that obtain again.It is as follows to measure the biologically active result:
Table 5 sample A, B are to the tagging of cabbage caterpillar, antifeedant activity
| Flow point | Concentration (mg/l) | Corrected mortality (%) | Food refusal rate (%) | ||
| 24h | 48h | 72h | 24h | ||
| The A sample | 4.092×1000 1.023×1000 2.558×100 8.525×10 | 90 50 15 0 | 100 70 20 0 | 80 25 0 | 100 98 88 80 |
| The B sample | 4.080×1000 1.020×1000 2.505×100 8.350×10 | 80 55 20 0 | 100 75 30 0 | 80 40 0 | 100 97 89.2 84.5 |
As shown in Table 5, two samples have all shown insecticidal activity preferably, during 72h, and the lethal concentration of 50 (LC of sample A contact toxicity
50) be 530.3mg/L; 72h, the lethal concentration of 50 (LC of the contact toxicity of sample B
50) be 483.4mg/L.Simultaneously, shown stronger antifeedant activity.
Embodiment 3 active substance structures are identified
Compd A
Compd A is faint yellow oily thing, is soluble in organic solvents such as benzinum, chloroform, ethyl acetate, is the bluish violet spot under the ultra-violet analysis lamp on the silica GF254 thin layer.Spectral data is analyzed as follows:
Uv λ max (methyl alcohol) nm:283.0,309.0 (weak).The weak peak at ultraviolet absorption peak 309.0nm place is the n → π of (carbonyl)
*Transition, ultraviolet absorption peak 283.0 is π → π
*Transition.
IR ν max cm
-1: 3400.81 (hydroxyl, blunt type peaks), 3027.84 (phenyl ring hydrogen), 2930.28,2858.62 (saturated hydrogen), 1682.26 (carbonyls), 1598.67,1581.49,1496.20,1450.86,753.90,699.65 (single-substituted rings).
1H-NMR (CDCl
3, 600Hz) (2H dm) is 4 H, δ 2.83 (2H to δ ppm:1.90, dm), be 5 H, δ 3.13 (2H, M), be 2 H, (1H m) is hydroxyl H to δ 3.95, δ 4.25 (1H, m) be 3 H, δ 7.19 (1H, the wide q of m) be 4 " position H; δ 7.24 (2H, wide q) be 2 "; 6 " position H, and δ 7.30 (2H is 3 t) "; 5 " position H, δ 7.47 (2H, t, J=7.8Hz) be 3 ', 5 ' H, δ 7.59 (1H, t J=7.8Hz) is 4 ' H, δ 7.94 (2H, t J=7.8Hz) is 2 ', 6 ' H.
(1) δ value
According to shoolery formula δ (CH
2)=0.23+ ∑ δ is according to formula δ (phenyl ring hydrogen)=7.27-Σ S
iCalculate the chemical displacement value of each H, be compared as follows with measured value again:
Table 6. δ value relatively
As seen from the above table, phenyl ring hydrogenation displacement study measured value and calculated value comparatively meet, because the influence of hydroxyl and carbonyl, the hydrogen on methylene and the methine all moves to low, but all within chemical shift separately.For hydroxyl hydrogen, because sample adopts alcohol extract, therefore may associate, so make and branch occurs splitting on the spectrogram with sample.
(2) J coupling and H number
δ=1.90 places are two groups of multiplets, are respectively that 2 hydrogen of 4 are influenced by 52 hydrogen and 3 hydrogen to split branch; δ=2.83 places are two groups of multiplets, and 2 hydrogen that are respectively 5 hydrogen are subjected to the influence of hydrogen on 42 hydrogen and the phenyl ring to split branch.δ=3.13 are four groups of doublets, are that 2 hydrogen are influenced by hydrogen and benzene ring hydrogen on 3 carbon to split branch, and δ=4.25 are one group of multiplet, are that 3 hydrogen are subjected to 2 to influence the multiple swarming that splits that produces with two kinds of different hydrogen of environment of 4 hydrogen.Aromatic ring hydrogen: δ 7.10～7.26 places are 2 ", 4 ", 6 " and broad peak that H overlaps, the H number is 3, δ=7.30 places are 3 ", 5 " two H split by both sides H to be divided into triplet.δ 7.47 3 ', 5 ' locates to be subjected to both sides H to split 1: 2: 1 triplet of branch, and δ=7.59 are 4 ' and are subjected to 3 ', 5 ' two 2 H (A
2System) splits the triplet of branch.δ=position, 7.94 place 2 ', 6 ' H is subjected to 3 ' or 5 ' H to split 1: 1 the doublet in branch position.
13C-NMR (CDCl
3, 400Hz) δ ppm:31.807 (C-5), 38.081 (C-4), 44.976 (C-2), 67.645 (C-3), 107.919～178.415 (12C, the C signals on the phenyl ring), 200.887 (carbonyl carbon)
13The C concrete analysis:
The carbonyl carbon chemical displacement value can be defined as ketone group at 200 places, has confirmed the carbonyl peak in the INFRARED SPECTRUM.
According to formula δ (aromatic ring C)=128.5+ Σ A
i, δ (alkane C)=-2.6+ Σ n
IjA
j+ Σ S
iCalculate the chemical displacement value of each carbon, compare with measured value, the result is as follows:
Table 7: the δ value relatively
As seen from the above table, each chemical displacement value and calculated value meet, owing to be subjected to the influence of carbonyl and hydroxyl skew are arranged slightly, but in the normal range (NR) of chemical shift separately.
According to mass spectral analysis, must molecular formula be: C
17H
18O
2Degree of unsaturation Ω
＝1+n
4+(n
3-n
1+3n
5)/2＝1+17-18/2＝9
Comprehensive spectrum and Spectrum Analysis, compd A is 1,5-diphenyl-3-hydroxyl-1-pentanone, to obtain the product qualification result identical with method by organic synthesis.
Compd B
Compd B is shallow milk yellow crystal, is soluble in organic solvents such as benzinum, chloroform, ethyl acetate, does not develop the color under uviol lamp, develops the color in iodine vapor and sulfuric acid-alcohol solvent.Spectral data is analyzed as follows:
Uv λ max (methyl alcohol) nm:208.0,285.0 (weak).Can infer tentatively that wherein containing aldehyde ketone gets carbonyl or conjugation carbonyl.
IR ν max cm
-1: there is broad peak at 3368.34,3306.58 places, (υ
-OHStretching vibration peak owing to have hydrogen bond between carbonyl, make bands of a spectrum shift to low frequency, and peak shape broadens)
2920.33，2853.16(υc＝C-H，S)，1711.63(υc＝O，S)，1463.69，1411.79，1379.10(δ
CH，m)，1258.50，1072.94(υc＝O，m)，723.96(δ
CH，w)
1H-NMR (CDCl
3, 600Hz) δ ppm:0.89 (m) is a methyl hydrogen, 2.35 (t) are
, be subjected to the next door methylene to influence to split and be divided into triplet.Many groups peak is arranged at 1.20～2.10 places, be the peak of methylene or methine hydrogen.
13C-NMR (CDCl
3, 400HZ) δ ppm:179.408 is
, 129.237,127.991 is double key carbon.Be the above cycloalkane of five-membered ring about 26,14 is methyl carbon.
EI-MS
M/z (%)According to isotope and M
+Ion analysis is looked into Beyon and is shown to such an extent that molecular formula is C
18H
32O
3. Ω=1+n
4+ 1/2 (n
3-n
1+ 3n
5)=1+18-32/2=3. has M-17[-OH (R)], M-26[
], M-45[
]
Determine that the compd B structure is 4-hydroxy sesquiterpene propyl ester (4-Hydroxy-Sesquiterpene-propylene-ester),
The preparation of embodiment 4 agricultural chemicals of the present invention
N-hexane extract 100g of the present invention is mixed with mass ratio with methyl-sulfoxide, missible oil at 1: 1: 2, mix, promptly get and resist the cabbage caterpillar agricultural chemicals with ultrasonic is fully emulsified.Be diluted with water to 33-50L during use, making extract concentrations is about 2000-3000mg/L.
The preparation of embodiment 5 agricultural chemicals of the present invention
The compounds of this invention 12.5g is mixed with mass ratio with methyl-sulfoxide, missible oil at 1: 1: 2, mix, promptly get and resist the cabbage caterpillar agricultural chemicals with ultrasonic is fully emulsified.Be diluted with water to 12.5-25L during use, the concentration that makes compd A is about 500-1000mg/L.
The preparation of embodiment 6 agricultural chemicals of the present invention
The compounds of this invention 25g is mixed with mass ratio with methyl-sulfoxide, missible oil at 1: 1: 2, mix, promptly get and resist the cabbage caterpillar agricultural chemicals with ultrasonic is fully emulsified.Be diluted with water to 12.5-17L during use, making compd B concentration is about 1500-2000mg/L.
In sum, Chinese Stellera Root n-hexane extract provided by the invention, compd A, compd B etc. are all to having stronger poisoning and antifeedant activity to cabbage caterpillar, it is fast to be with it that agricultural chemicals of insecticide active substance has drug effect, the term of validity is long, quality controllable characteristics, for agricultural provides a kind of high-efficiency low-toxicity, noresidue, new insecticide pesticide free from environmental pollution is selected.
Claims (4)
1, the purposes of compd B in insecticide pesticide,
Compd B 4-hydroxy sesquiterpene propyl ester.
2, according to the described purposes of claim 1, it is characterized in that: described insecticide pesticide is anti-cabbage caterpillar agricultural chemicals.
3, a kind of insecticide pesticide, it is to be that active component is prepared from by compd B, it contains the compd B of 150-2000mg/L.
4, a kind of insecticide pesticide, it is to be that active component is prepared from by compd A and compd B, it contains the compd B of 1500～2000mg/L and the compd A of 500～1000mg/L,
Compd A 1,5-diphenyl-3-hydroxyl-1-pentanone.
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| CNB2006100795930A CN1331838C (en) | 2005-07-27 | 2005-07-27 | Pesticide uses of compound 4-hydroxy sesquiterpene propyl ester |
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| CN 200510021333 Division CN1285263C (en) | 2005-07-27 | 2005-07-27 | Preparation of pesticide active matter in stellera chamejasme and use |
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| CN1331838C CN1331838C (en) | 2007-08-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102578094A (en) * | 2011-01-13 | 2012-07-18 | 中国中化股份有限公司 | Use of (+)- epiafzelechin as pesticide |
| CN107183025A (en) * | 2017-05-08 | 2017-09-22 | 青岛农业大学 | A kind of application of naphthalene nucleus type sesquiterpenoid |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS617201A (en) * | 1984-06-20 | 1986-01-13 | Sumitomo Chem Co Ltd | Fungicide |
| US5578637A (en) * | 1995-05-03 | 1996-11-26 | University Of Washington | Methods of inhibition or killing cancer cells using an endoperoxide |
| CN1209967C (en) * | 2002-10-28 | 2005-07-13 | 四川大学 | Euphorbia-one pesticide and preparing method thereof |
-
2005
- 2005-07-27 CN CNB2006100795930A patent/CN1331838C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102578094A (en) * | 2011-01-13 | 2012-07-18 | 中国中化股份有限公司 | Use of (+)- epiafzelechin as pesticide |
| CN107183025A (en) * | 2017-05-08 | 2017-09-22 | 青岛农业大学 | A kind of application of naphthalene nucleus type sesquiterpenoid |
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