CN1331838C - Pesticide uses of compound 4-hydroxy sesquiterpene propyl ester - Google Patents

Abstract

The present invention provides an application for active compound A, B in pesticide by further separating stellera chamaejasme hexane extractant. Through using cabbage caterpillars as target insects, the biological activity test result indicates that when the radix hexane extractant is diluted into 30 times, the corrected mortality of the cabbage caterpillars for 72 hours is 100 percent, the contact activity of the compound A (1, 5-diphenyl-3-hydroxyl-1-pentanone) for the cabbage caterpillars is 483.4 mg/L (LC50), and the contact activity of the compound B (4-hydroxy-sesquiterpene-propylene-ester) for the cabbage caterpillars is 530.3 mg/L (LC50). The present invention further lays the foundation for using stellera chamaejasme to create novel non-pollution plant pesticide.

Description

The pesticide uses of compound 4-hydroxy base sesquiterpene propyl ester

The application is that denomination of invention is The preparation of insecticide active substance and purposes in the Stellera chamaejasme L., 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 Stellera chamaejasme L. 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 residue, economic biological pesticide 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.

Stellera chamaejasme L. (StellerachanlaejastneL.), the red root of langdu, silk floss wipe out greatly, one perfume, red match end, Graceful Jessamine Herb.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, lymphoid tuberculosis, 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 biological pesticide-vegetable insecticide, this sterilant insect is had tags, stifling and stomach poison function.And it is fast to have drug effect, and validity period is long, high-efficiency low-toxicity, and noresidue, free from environmental pollution, do not destroy advantages such as the eubiosis, no resistance.Xie Qingke report root of langdu solution spray, can prevent and treat cabbage caterpillar, aphid, eating-core bean worm, two-spotted spider mite, agrotis, loose high and steep moth, pine moth, 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 farm crop, 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 extraction to tagging of cabbage caterpillar etc., does not see the report that uses n-hexane extract at present, and report extract activeconstituents portion clear and definite.At present, mainly getting from Stellera chamaejasme L. is flavonoid and coumarin kind compound; Liu Gui virtue etc. is also told β-Gu Zaichun, daucosterol compounds such as (Daucostero1) from the auspicious root of langdu in addition.[Feng Baomin, Pei Yuehu, Han Bing, " Stellera chamaejasme L. chemical constitution study ", Shenyang Pharmaceutical University's journal, 2000,17 (4), p258-259] three compounds identifying are disclosed, comprising compd A 1,5-phenylbenzene-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 Stellera chamaejasme L. n-hexane extract in insecticide pesticide.Contain among compd A, the B one or more in the described Stellera chamaejasme L. n-hexane extract.

Compd A 1,5-phenylbenzene-3-hydroxyl-1-pentanone

Compd B 4-hydroxy sesquiterpene propyl ester

It is the agricultural chemicals of main active ingredient that the present invention also provides with Stellera chamaejasme L. n-hexane extract, compd A, compd B.Described agricultural chemicals can be to be that activeconstituents is prepared from by the Stellera chamaejasme L. 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 Stellera chamaejasme L. 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 stationary phase is a silica gel H;

A, huge pillar rough segmentation

Stationary phase: silica gel H; 1), normal hexane-ethyl acetate-methylene dichloride (volume ratio is 1: 1: 1) moving phase: (volume ratio is 20 ~ 1: with normal 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

Stationary 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, the section 3 is gone up sample 58 at every turn; Flow velocity 2.5ml/min, 1), normal hexane-ethyl acetate-methylene dichloride (volume ratio is 1: 1: 1), methylene dichloride-ethyl acetate-methyl alcohol (volume ratio is 10: 10: 2) moving phase: (volume ratio is 10～1: with normal hexane-ethyl acetate; Gradient elution, fraction collection merges R after thin-layer chromatography detects _rBe 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 biological activity, carry out next step column chromatography segmentation.

C, pillar segmentation

Stationary 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; Moving phase: with normal hexane-ethyl acetate (volume ratio is 4: 1), methylene dichloride-ethyl acetate (volume ratio is 1: 1); Gradient elution merges after thin-layer chromatography detects, and is used for biological activity determination, and the biological activity that gets pillar section 2 is the highest.Still have 2 bands of a spectrum in section 2, changing the eluent condition can't separate, so adopt reversed phase column chromatography to carry out next step separation.

D, reverse phase silica gel post separate

Stationary 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, each 2g; Moving phase: methanol-water-tetrahydrofuran (THF) (volume ratio is (10～20): (2～5): (3～7)), methyl alcohol-tetrahydrofuran (THF) (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 Stellera chamaejasme L. 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 dehydrated 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 Stellera chamaejasme L. 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 residual adsorption impurity, experiment shows that huge pillar just divides very good to rough segmentation extract subsection efect, one step can improve effective constituent 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.

Small white Pieris rapae Linnaeus, English name: cabbage butterfly, popular name Lai Bai butterfly, sulphur butterfly, larva another name cabbage caterpillar.Belonging to the lepidopteran Sulfur butterfly, promptly is the larva of Lay white butterfly to the blue or green worm of the Lay 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 blue or green worm resistance of Lay to strengthen,, form vicious cycle to such an extent as to have to strengthen dosage and number of times, cause in the vegetables pesticide residue big, influence vegetables quality, jeopardize HUMAN HEALTH etc.

Evidence, when Stellera chamaejasme L. n-hexane extract provided by the invention diluted 30 times, in the 72h was 100% to the cabbage caterpillar corrected mortality, the median lethal concentration(LC﹠-{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 effective constituent, 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-phenylbenzene-3-hydroxyl-1-pentanone ₅₀); And compd B: 4-hydroxy sesquiterpene propyl ester (4-Hydroxy-Sesquiterpene-Propylene-Es ter), its contact toxicity to the blue or green worm of Lay is 530.3mg/L (LC ₅₀).

In a word, pesticide efficacy provided by the invention is fast, validity period 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, eating-core bean worm, two-spotted spider mite, agrotis, loose high and steep moth, pine moth, 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 synoptic diagram;

The separation and purification synoptic diagram of Fig. 2 Stellera chamaejasme L. 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

Stellera chamaejasme L. picks up from Ruoergai grassland, Sichuan Province, and the fresh Stellera chamaejasme L. root that collection is returned is cleaned and dried, and pulverizes with pulverizer, obtains fine hair shape root of langdu powder.

Take by weighing a certain amount of Stellera chamaejasme L. 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 normal hexane, chloroform, ethyl acetate, methyl alcohol respectively again, obtains the opposed polarity extract, repeat 3 times to extracting fully, merge identical extraction liquid.

According to the method that Zhang ZongBing introduces, adopt antifeedant activity and contact toxicity to measure virulence simultaneously: at first do not gather the blue or green worm of Lay 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 wave, water dilution constant volume is as treatment solution, 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 punch tool (diameter 2cm), treatment solution and contrast liquid are pressed gradient dilution to cabbage caterpillar.Feed to cabbage caterpillar in the treatment group leaf dish that treatment solution 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 dish 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 solution 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	Concentration (mg/L)	Corrected mortality (%)			Food refusal rate (%)
						24h	48h	72h	24h
		The dehydrated alcohol extraction thing	5×1000	75.2	87.7					94.2	99.2
2.5×1000	57.8					76.8	86.8	91.3
			1.25×1000	43.7	69				81.2	70.7
6.25×100	25					44.2	55.7	52
			N-hexane extract	11.11×1000	75				87.5	100	100
3.703×1000	50	67.5				87.5	100
				1.234×1000	37.5			50	50	100
4.113×100	25	25				37.5	100
				Chloroform extract	11.11×1000			6.5	7.5	18.8	80
3.703×1000	0	2.5	6.3			50
					1.234×1000		0	0	0	33.3
4.113×100	0	0	0			10
					Acetic acid ethyl ester extract		8.000×1000	12.5	25	30	50
4.000×1000	10.3	21.3	25	37.5
						2.000×1000	0	12.5	18.8	25
1.000×1000	0	6.8	12.5	12.5
						The methanol extraction thing	7.711×1000	37.5	50	55.6	50
3.855×1000	33.3	40	47.5	45
					1.928×1000		25	37.8	41.3	25
9.638×100	0	6.7	16.7	25

As can be seen from Table 1, the contact toxicity of N-hexane extract is the highest, 72h median lethal concentration(LC﹠-{50}) (LC ₅₀) be 812.1mg/L, the methanol extraction thing is secondly; In test food refusal rate, the biological activity 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 chromatographic separation purifying of embodiment 2 Stellera chamaejasme L. deinsectization active substances

Make the adsorption chromatography stationary phase 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 hour for 105 ℃, leaves in the moisture eliminator stand-by after the cooling.With point sample kapillary point sample, the mixed solvent of forming different ratios with the difference of normal hexane, chloroform, ethyl acetate, methylene dichloride, methyl alcohol equal solvent is a developping agent 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 normal hexane-ethyl acetate (volume ratio is 20: 1), adopt gradient elution, increase polarity gradually, to normal hexane-ethyl acetate-methylene dichloride (volume ratio is 1: 1: 1) as initial 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 the blue or green worm of Lay, antifeedant activity

Flow point	Concentration (mg/l)	Corrected mortality (%)			Food refusal rate (%)
						24h	48h	72h	24h
		Huge pillar 1	43.32×1000	62.5	68.8					75	50
10.83×1000	18.8					43.8	50	20
			2.708×1000	12.5	12.5				18.8	11.1
6.769×100	0					12.5	12.5	9.1
			Huge pillar 2	48.55×1000	100						100
12.14×1000	93.8	93.8				100	95
				3.034×1000	56.3			62.5	68.8	90
7.586×100	43.8	50				55	85
				Huge pillar 3	40.00×1000			100			100
10.00×1000	90	95	100			95
					2.500×1000		56.7	75	80	80
6.250×100	27.3	45.5	54.6			50

Section 1 contains 3 bands of a spectrum approximately, and section 2 contains 3 bands of a spectrum approximately, and section 3 contains 3 bands of a spectrum approximately, and both have 1 intersection bands of a spectrum the back.Biological activity determination is the result show, section 2 performances are active preferably, so, merge section 2, section 3, further separation and purification.

The center pillar segmentation

Adopt normal hexane-ethyl acetate (volume ratio is 10: 1,4: 1,1: 1), normal hexane-ethyl acetate-methylene dichloride (volume ratio is 1: 1: 1), methylene dichloride-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)	Corrected mortality (%)			Food refusal rate (%)
						24h	48h	72h	24h
		Center pillar 1	5.684×1000	10	20					26.7	20.7
1.421×1000	6.7					13.3	20	11.1
			3.553×100	5.5	10.1				13.3	6.7
8.881×10	0					0	0	3.3
			Center pillar 2	5.951×1000	66.7				87.8	93.3	100
1.488×1000	20	40				66.7	100
				3.719×100	6.7			13.3	26.7	78.3
9.289×10	6.7	6.7				13.3	52.9
				Center pillar 3	4.763×1000			50	60	70	100
1.191×1000	30	37.5	45			90
					2.977×100		6.7	13.3	18.8	60
7.442×10	0	0	0			50

The result shows that section 2 has biological activity preferably, proceeds little column separating purification.

The pillar segmentation

Adopt normal hexane-ethyl acetate (volume ratio is 4: 1), methylene dichloride-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 the blue or green worm of Lay, antifeedant activity

Flow point	Concentration (mg/l)	Corrected mortality (%)			Food refusal rate (%)
						24h	48h	72h	24h
		Pillar 1	4.173×1000	50	60					70	100
1.043×1000	20					40	50	95
			2.608×100	0	10				10	90.5
8.694×10	0					0	0	73.9
			Pillar 2	4.092×1000	90				100		100
1.023×1000	40	70				80	98
				2.558×100	0			6.7	13.3	88.2
8.525×10	0	0				0	87.8
				Pillar 3	5.571×1000			30	45	70	100
1.393×1000	20	40	50			97
					3.482×100		5	20	30	77.8
1.161×10	0	0	0			60

Section 1 contains 1 bands of a spectrum approximately, and section 2 has 2 bands of a spectrum, and section 3 has 2 bands of a spectrum.Section 2, section 3 have the intersection bands of a spectrum.Binding bioactive is measured, and section 2 is gone up the reverse phase silica gel post again, and the separation that once goes on foot is purified.

The reverse phase silica gel post separates

Adopt methanol-water-tetrahydrofuran (THF) (volume ratio is 16: 4: 5), methyl alcohol-tetrahydrofuran (THF) (volume ratio is 1: 1); Gradient elution, the reverse phase silica gel thin plate detects, and developping agent is methanol-water-tetrahydrofuran (THF) (volume ratio is 16: 4: 5), and detected 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 biological activity result:

Table 5 sample A, B are to the tagging of the blue or green worm of Lay, antifeedant activity

Flow point	Concentration (mg/l)	Corrected mortality (%)			Food refusal rate (%)
						24h	48h	72h	24h
		The A sample	4.092×1000	90	100						100
1.023×1000	50					70	80	98
			2.558×100	15	20				25	88
8.525×10	0					0	0	80
			The B sample	4.080×1000	80				100		100
1.020×1000	55	75				80	97
				2.505×100	20			30	40	89.2
8.350×10	0	0				0	84.5

As shown in Table 5, two samples have all shown insecticidal activity preferably, during 72h, and the median lethal concentration(LC﹠-{50}) (LC of sample A contact toxicity ₅₀) be 530.3mg/L; 72h, the median lethal concentration(LC﹠-{50}) (LC of the contact toxicity of sample B ₅₀) be 483.4mg/L.During with `, 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 sherwood oil, chloroform, ethyl acetate, is the bluish voilet 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.

IRvmax 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-∑ S _iCalculate the chemical displacement value of each H, be compared as follows with measured value again:

Table 6: the 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 radical and the methyne all moves to low, but all within chemical shift separately.For hydroxyl hydrogen, because sample adopts extraction using alcohol, 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+ ∑ A _i, δ (alkane C)=-2.6+ ∑ n _IjA _j+ ∑ 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 of chemical shift separately.

According to mass spectroscopy, 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-phenylbenzene-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 sherwood oil, chloroform, ethyl acetate, does not develop the color under ultraviolet 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.

IRvmax 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 radical 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 radical or methyne hydrogen.

¹³C-NMR (CDCl ₃, 400HZ) δ ppm:179.408 is

129.237 127.991 is double key carbon.Be the above naphthenic hydrocarbon of five-ring about 26,14 is methyl carbon.

EI-MS _M/zn3According to isotropic substance 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 ₂-n ₄+ 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-sulphoxide, missible oil at 1: 1: 2, mix, promptly get and resist the cabbage caterpillar agricultural chemicals with ultrasonic wave is fully emulsified.Be diluted with water to 33-50L during use, making extract concentrations is about 2000-30000mg/L.

The preparation of embodiment 5 agricultural chemicals of the present invention

The compounds of this invention A12.5g is mixed with mass ratio with methyl-sulphoxide, missible oil at 1: 1: 2, mix, promptly get and resist the cabbage caterpillar agricultural chemicals with ultrasonic wave 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 B 25g is mixed with mass ratio with methyl-sulphoxide, missible oil at 1: 1: 2, mix, promptly get and resist the cabbage caterpillar agricultural chemicals with ultrasonic wave is fully emulsified.Be diluted with water to 12.5-17L during use, making compd B concentration is about 1500-2000mg/L.

In sum, Stellera chamaejasme L. 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, validity period 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 (3)

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 contains the compd B of 1500～2000mg/L.

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