CN101205222A - Total synthesis of Rocaglamide and uses thereof as insecticidal agent - Google Patents
Total synthesis of Rocaglamide and uses thereof as insecticidal agent Download PDFInfo
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- CN101205222A CN101205222A CNA2006101654520A CN200610165452A CN101205222A CN 101205222 A CN101205222 A CN 101205222A CN A2006101654520 A CNA2006101654520 A CN A2006101654520A CN 200610165452 A CN200610165452 A CN 200610165452A CN 101205222 A CN101205222 A CN 101205222A
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Abstract
The invention relates to a excellent natural botanical source insecticide called rocaglamide (structural formula 1), a synthesis method and application as agricutural insecticides. The compound is synthesized adopting the following route: a compound 1 has an excellent killing effects on cabbage caterpillars, diamondback moths, beet armyworms and cotton bollworms, and has outstanding repellent activity over the diamondback moths.
Description
Technical field
The present invention relates to the preparation method and the application of a class natural phant botanical pesticide chinaberry acid amides (Rocaglamide).
Background technology
Natural compounds often shows various unique biological activity, and this makes it become searching and screens the natural treasure-house of various biologically active substances as medicine, agricultural chemicals etc., also is the desirable first guide structure source of development of new biologically active substance.To be nineteen eighty-two by Ming etc. separate from Melia plant Aglaia elliptica chinaberry acid amides (rocaglamide) first obtains, and determines that with the X-ray diffraction method it has structure shown in 1, and confirm that it is wherein an activeconstituents.
Rocaglamide
(1)
Because the desinsection and the pharmacological action characteristic (leukemia etc.) of this compound brilliance, complete synthesis and structure derivatize has carried out a lot of researchs to it in more external research groups, set up some total synthesis methods, but all there are problems such as route is long, yield is low in these methods.The present invention has set up a kind of method that is short, synthetic racemize chinaberry acid amides that yield is higher, that be suitable for suitability for industrialized production.
Disclosure of the Invention
An object of the present invention is to provide novel pentamethylene of a class and cumarone.
Pentamethylene provided by the present invention and benzofuran compounds, name be called racemize chinaberry acid amides (± rocaglamide) and the racemic mixture of the diastereomer of chinaberry acid amides.Its synthetic route is as follows:
This compound has excellent insecticidal activity and insect repellant activity.
The present invention can be described further with following example, but is not limited only to these examples.
Synthesizing of example 1.4-methoxyl group-Cyanobenzyl Alcohol
In being furnished with churned mechanically 500mL there-necked flask, add 180mL water and 17.0g (0.163moL) NaHSO
3, stir and make its dissolving, be heated to 40 ℃, add 22g (0.162moL) aubepine then, behind the reaction 20min, be cooled to 0 ℃ with ice bath, add the 200mL ether, drip the 40mL aqueous solution that contains 9g NaCN (0.173moL) then, in 30min, add.With the reaction solution separatory, water is used 50mL extracted with diethyl ether twice respectively, merges organic phase, anhydrous CaCl
2Dry.Behind the precipitation the 22.3g white solid, m.p.43～44 ℃, yield 85.1%.
1H-NMR(CDCl
3)：δ3.21(d，1H，J＝6.0)，3.82(s，3H)，5.44(d，1H，J＝6.0)，6.93(d，2H，J＝8.8Hz)，7.42(d，2H，J＝8.8Hz)
IR(cm
-1)：3400，2980，2800，1620，1580，1520，1480，1420，1310，1250，1130，820，780，620.
Example 2.4, the preparation of 6-dihydroxyl-2-(4-methoxyphenyl) chromene-3 (2H)-ketone
In the 250mL there-necked flask, add 10.0g (61.7mmol) cyanohydrin, 8.5g (67.5mmol) Phloroglucinol monomethyl ether and 150mL anhydrous diethyl ether, stirring and dissolving postcooling to 0 ℃.Import exsiccant HCl gas, about 1.5h that ventilates has red precipitate to occur in the reaction flask.With the reaction solution cooling, filter, solid washes the final vacuum drying with water.Recrystallizing methanol gets product 10.3g, yield 61.3%.M.p.203～204 ℃ (literature value: 201～202 ℃, 76%)
1H-NMR：δ3.72(s，3H)，6.06(d，1H，J＝2Hz)，6.14(d，1H，J＝2Hz)，6.82(d，2H，J＝8.5Hz)，7.04(d，2H，J＝8.5Hz)
IR(cm
-1)：2980，1680，1620，1500，1450，1250，1180，1160，1070，1020，820，700.
Example 3.4, the preparation of 6-dimethoxy-2-(4-methoxyphenyl) chromene-3 (2H)-ketone
In the 250mL there-necked flask, add 12.2g (88.4mmol) Anhydrous potassium carbonate, 11.2g (89.0mmol) methyl-sulfate and 60mL acetone, behind the logical nitrogen 20min, add and contain 6g (22.1mmol) 4, the 90mL acetone soln of 6-dihydroxyl-2-(4-methoxyphenyl) chromene-3 (2H)-ketone, behind the reflux 0.5h, add 25mL methyl alcohol, continue heating reflux reaction 1h, cooling, filter, solid washes the final vacuum drying with water, and recrystallizing methanol gets target compound 5.76g, yield 87.0%, m.p.121～122 ℃.
1H-NMR(CDCl
3)：δ3.79(s，3H)，3.88(s，3H)，3.90(s，3H)，5.43(s，1H)，6.04(d，1H，J＝1.8Hz)，6.22(d，1H，J＝1.8Hz)，6.87～6.90(d，2H，J＝9Hz)，7.29～7.32(d，2H，J＝9Hz).
IR(cm
-1)：2980，1710，1620，1580，1500，1480，1250，1220，1110，810，800.
Example 4.4, the reaction of 6-dimethoxy-2-(4-methoxyphenyl)-2-cumarone-3-(2H)-ketone and α-methoxycarbonyl-methyl cinnamate
In the 250mL there-necked flask, add 3.00g (10mmol) raw material 4; 6-dimethoxy-2-(4-methoxyphenyl) chromene-3 (2H)-ketone; the anhydrous THF of 130mL; logical nitrogen protection; stirring and dissolving; be heated to 40 ℃, add the methanol solution that 0.3mL contains TritonB (40%) then, then add the THF solution that 40mL contains 3.2g (14.5mmol) benzene methene propylmalonic acid dimethyl ester.Insulation reaction 3h., cooling, precipitation, the column chromatography gradient elution, Michael adduct 2.74g, yield 52.6%, m.p.173～174 ℃.
C
29H
28O
9, MS
-(520.1735 theoretical value 520.1739).
MS：520(3.3)，300(25.0)，299(100)，191(3.3)，163(3.3)，135(13.0)，121(3.0)
1H-NMR(CDCl
3)δ：3.17(s，3H)，3.27(s，3H)，3.65(s，3H),3.77(s，3H)，3.86(s，3H)，4.33(d，1H，J＝10.8Hz)，4.53(d，1H，J＝10.8Hz)，5.78(d，1H，J＝1.8Hz)，6.27(d，1H，J＝1.8Hz)，6.82～6.85(m，2H)，7.05～7.13(m，3H，)，7.31～7.34(m，2H)，7.69～7.76(m，2H).
13C-NMRδ：194.4，174.1，169.6，167.7，167.6，159.7，159.2，135.5，130.0，127.8，127.6，127.4，127.0，113.4，103.8，92.9，92.4，88.5，55.9，55.8，55.3，54.2，52.3，52.2，51.5.
IR(cm
-1)：2980，1760，1740，1710，1620，1600，1500，1480，1450，1420，1320，1230，1150，1040，820，720
Example 5. reductive coupling reactions
In the 250mL there-necked flask, add 1.50g (10mmol) samarium metal, logical nitrogen 15min adds and contains C
2H
4l
21.41g THF solution (7.5mmol), stir 1h, the solution becomes au bleu, reaction solution continues ultrasonic response 3h, adds the 100mL benzole soln that contains the 1.30gMichael adduct, behind the reaction 10h, the hydrochloric acid soln that adds the 1mol/L of 20mL, stir, reaction solution becomes settled solution, separates back water layer CH
2Cl
2Extraction is with saturated nacl aqueous solution washing, anhydrous Na
2SO
4Drying, column chromatography for separation behind the precipitation, product reductive coupling product 0.41g, yield 33.3%.m.p.163～164 ℃.
MS：472(6.0)，414(4.6)，300(100)，285(26.6)，269(3.0)，242(3.0)，135(10.0)，104(3.0)，77(3.0)，44(7.3)
1H-NMR(CDCl
3)：δ3.04(s，1H)，3.66(s，3H)，3.71(s，3H)，3.81(s，3H)，3.85(s，3H)，4.06(d，1H，J＝13.2Hz)，4.24(d，1H，J＝13.2Hz)，6.10(d，1H，J＝1.8Hz)，6.35(d，1H，J＝1.8Hz)，6.66～6.70(m，2H)，6.89～6.97(m，4H，)，7.08～7.12(m，3H).
13C-NMR：δ203.3，167.2，164.9，161.0，158.9，158.6，135.4，129.1，128.0，127.9，127.7，127.1，125.4，113.2，112.2，106.1，99.3，92.9，89.9，88.5，56.4，55.7，55.6，55.1，55.0，52.9，52.0，51.5.
IR(cm
-1)：3420，2980，1760，1720，1620，1600，1520，1480，1260，1230，1180，1160，1120，1100，1020，820，710.
Example 6. aminolysis reactions
In 50mL single port bottle, vacuumize and nitrogen replacement three times, the anhydrous THF that adds 8mL, be cooled to-78 ℃, the butyllithium 1.2ml (3mmoL) that adds 1.07g (23.8mmoL) dimethylamine and 2.5M then, continue reaction 20min down at-78 ℃, add the THF solution 6mL that contains 0.15g (0.31mmoL) reductive coupling product then.Continue reaction 30min at-78 ℃, be warming up to room temperature then and react 50min.In reaction solution, add 2mL methyl alcohol, slowly drip the HCl solution 15mL of 1moL/L then.Reaction solution CH
2Cl
2Extraction, saturated nacl aqueous solution washing, anhydrous Na
2SO
4Drying, column chromatography for separation behind the precipitation, aminolysis product 0.13g, yield 84.4%, m.p.143～144 ℃.
MS：485(25.3)，458(2)，414(8)，300(100)，285(19.3)，176(3.3)，131(7.3)，103(3.3)，72(5.0)
1H-NMR(CDCl
3)δ：2.90(s，3?H)，3.01(s，1H)，3.25(s，3H)，3.73(s，3H)，3.80(s，3H)，3.84(s，3H)，4.33(d，1H，J＝13.2Hz)，4.51(s，1H，J＝13.2Hz)，6.08(d，1H，J＝1.8Hz)，6.32(d，1H，J＝1.8Hz)，6.70～6.73(m，2H)，6.82～6.85(m，2H)，6.98～7.01(m，2H)，7.07～7.09(m，3H)
13C-NMRδ：205.7，165.3，164.8，161.1，158.9，158.5，136.2，128.0，127.9，126.9，126.1，113.2，106.2，99.3，93.0，89.9，88.6，55.6，55.1，53.9，52.0，37.7，36.2
IR(cm
-1)：3450，3010，2980，1630，1530，1510，1480，1450，1260，1220，150，1120，1060，1020，830，710
Synthesizing of example 7. chinaberry acid amides
In 100mL single port bottle, add 0.45g (1.71mmoL) Me
4NBH (OAc)
3, vacuumize and replace nitrogen three times after, add 1mL acetonitrile and 1mL acetate, behind the stirring reaction 0.5h, drip the acetonitrile solution 2.5mL of 0.12g (0.24mmoL) aminolysis product under the room temperature, continue stirring reaction 24h under the room temperature.In reaction solution, add the saturated NaHCO of 50mL
3Solution.Reaction solution CH
2Cl
2Extraction, saturated nacl aqueous solution washing, anhydrous Na
2SO
4Drying, column chromatography for separation behind the precipitation, target compound racemize chinaberry acid amides 0.106g, yield 88.3%m.p.120～122 ℃.
Racemize chinaberry acid amides: C
29H
29NO
7, M
+: 505.2104 (theoretical values 505.210)
MS(％)：505(12.0)，487(10.0)，442(5.3)，416(19.3)，390(60.7)，368(4.7)，325(4.0)，313(61.3)，285(22.0)，269(6.0)，243(7.3)，223(4.7)，205(26.7)，181(41.3)，176(100)，148(5.3)，131(16.7)，116(18.0)，91(3.7)，72(27.3)，46(6.7)
1H-NMR(CDCl
3)：δ2.94(s，3H)，3.31(s，3?H)，3.70(s，3H)，3.83(s，3H)，3.85(s，3H)，4.05(dd，1H，J＝13.5，J＝6.5)，4.55(d，1H，J＝13.5Hz)，4.93(d，1H，J＝6.5Hz)，6.10(d，1H，J＝Hz)，6.27(d，1H，J＝1.8Hz)，6.65～6.70(m，2H)，6.84～6.87(m，2H)，7.01～7.13(m，5H).
13C-NMR(CDCl
3)：δ169.6，163.9，161.1，158.6，157.3，137.6，128.9，127.8，127.7，127.1，126.3，112.7，107.6，101.7，94.1，92.5，89.3，78.6，?56.0，55.7，55.1，47.6，37.0，35.8.
IR(cm
-1)：3450，3010，2980，1630，1530，1510，1480，1450，1260，1220，150，1120，1060，1020，830，710
Can make the racemize diastereomer of chinaberry acid amides with method: yield 86.0%, m.p.＞200 ℃,
29H
29NO
7, M
+: 505.2105 (theoretical values 520.1739)
MS(％)：505(10.0)，487(9.3)，469(2.0)，442(4.0)，415(6.7)，390(95.3)，313(100)，285(23.3)，271(2.7)，243(10.0)，222(2.7)，205(20.0)，181(46.0)，176(74.0)，148(7.3)，135(18.7)，116(47.3)，91(5.0)，72(30.0)，46(12.0)
1H?NMR(CDCl
3)：δ2.85(s，3H)，2.99(s，3H)，3.58(1H，J＝10Hz，J＝12.2Hz)，3.78(s，3H)，3.82(s，3H)，3.83(s，3H)，4.24(d，1H，J＝12.2Hz)，4.81(dd，1H?J＝10Hz.)，6.10(d，1H，J＝2.0Hz)，6.20(d，1H，J＝2.0Hz)，6.84～6.89(m，2H)，6.99～7.02(m，2H)，7.13～7.17(m，3H)，7.37～7.42(m，2H)
13C?NMR(CDCl
3)δ：171.4，163.7，161.9，159.2，157.9，135.8，129.3，129.2，128.3，127.8，126.9，113.4，105.7，99.9，92.4，91.7，88.6，?84.7，55.7，55.6，55.2，54.8，47.3，37.4，36.0.
IR(cm
-1)：3440，3020，3300，2980，1630，1600，1510，1490，1460，1420，1250，1220，1200，1150，1120，1030，1000，800，690.
-
The desinsection and the insect repellant activity of example 8. racemize chinaberry acid amides and racemize diastereomer thereof
1 materials and methods
1.1 reagent agent
2 of test samples compare medicament with the female medicine of 10% nimbin (Chengdu green gold biotechnology company product).
1.2 test insect
Farm, the Chinese Academy of Agricultural Sciences Institute of Plant Protection, Haidian District, Beijing City cabbage field is directly picked up from small cabbage moth Plutella xylostella (Linnaeus) worm source.Test worm attitude is 3 instar larvaes.Beet armyworm and bollworm are the indoor feeding population, and test worm attitude is 3 instar larvaes.
1.3 toxicity test method
Medicament preparation: the investigational agent sample is mixed with 1% mother liquor earlier with chloroform, again mother liquor is diluted to the mensuration soup with the emulsifying agent and the aqueous solution that contains the 0.05%-triton x-100.
The repellent activity determination test: the examination worm is a small cabbage moth.With rape leaf with flushing with clean water, dry, being cut into diameter is the 70mm disk, is cut into two halfround bar slices again, one of them halfround bar slice tow sides is coated with the 0.2mL soup respectively, be coated with earlier during smear the one side, be coated with another side again after waiting to dry.Another halfround bar slice is made same processing the, blade in contrast with the aqueous solution of 0.05%-triton x-100.Treat after blade dries two halfround bar slices to be put into culture dish (diameter is 85mm, puts the filter paper of a slice diameter 70mm at the bottom of the ware in advance), stand-by.3 instar larvaes are inserted on the semi-circular blades of coating in the culture dish, every ware connects 10, seals, adds a cover with preservative film.Each concentration repeats 3 times.Check result after in (27 ± 1) ℃ illumination box, keeping 24～48 hours.Borer population in the statistics culture dish on two semi-circular blades calculates repellent effect.
Scattering ratio (%)=[(on the contrast leaf on borer population-chemicals treatment leaf borer population)/total borer population] * 100
The insecticidal activity assay test: cabbage caterpillar, small cabbage moth and beet armyworm are the baud spray method, respectively spray 1ml/ time in the two sides.Cabbage caterpillar, small cabbage moth were 3 ages for examination worm length of time, and beet armyworm was 2 ages for examination worm length of time.Bollworm connects the worm method for soaking leaf, and it is 15 millimeters sequins that blade is broken into diameter with punch tool, and dipping is 10 seconds in soup, dries, and it is put in every hole a slice in the 10 hole test boxs again.Bollworm 3 instar larvaes are inserted in the test box, and every Kong Yitou seals, adds a cover with preservative film.Each concentration is handled 10, repeats 6 times.If blank.
Be put in after the chemicals treatment and keep in (27 ± 1) ℃ illumination box checking mortality ratio after 72 hours.Dead judging criterion: to touch polypide reactionless or to react inharmonious person be death with dialling pin.
2 results and analysis
2.1 repellent activity to small cabbage moth
The repellent activity measurement result sees Table 1.
Table 1 test sample is to the repellent activity measurement result of small cabbage moth
Test-results shows, racemize chinaberry acid amides is under 100 and 200 μ g/mL concentration, repellent activity reaches 63.7% and 71.9% respectively, chinaberry acid amides diastereomer is under 100 and 200 μ g/mL concentration, repellent activity reaches 60% and 70.9%, two sample respectively small cabbage moth has been shown tangible repellent activity.On testing data, the repellent activity of two test samples is higher than contrast medicament nimbin, but test of significance shows that the scattering ratio difference under same concentrations is not remarkable between the three.
2.2 insecticidal activity to small cabbage moth, cabbage caterpillar, beet armyworm and bollworm
Insecticidal activity assay the results are shown in Table 2.From table 2 test-results as can be seen, racemize chinaberry acid amides is under the dosage of 200 μ g/mL and 100 μ g/mL, insecticidal effect to these 4 kinds of lepidoptera pests of cabbage caterpillar, small cabbage moth, beet armyworm and bollworm all is better than its racemize diastereomer, and also the effective of medicament nimbin shone in comparison.Test of significance also shows, has significant difference between racemize chinaberry acid amides, chinaberry acid amides racemize diastereomer and the contrast medicament nimbin under different using dosages.
Table 2 test sample to the insecticidal activities of 4 kinds of insects (corrected mortality, %)
The contrast mortality ratio: cabbage caterpillar and small cabbage moth are 0; Beet armyworm, 13.3%; Bollworm, 10.0%
Claims (4)
1. racemize chinaberry acid amides---a kind of compound with excellent insecticidal activity, its structural formula is:
2. the synthetic method of compound shown in the claim 1, its synthetic method is:
3. the method that is used for synthetic chinaberry amide derivatives or analogue shown in the claim 2.
4. compound shown in the claim 1 and be the application of the preparation made of activeconstituents or mixture as agricultural insecticide with it.
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| CNA2006101654520A CN101205222A (en) | 2006-12-20 | 2006-12-20 | Total synthesis of Rocaglamide and uses thereof as insecticidal agent |
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|---|---|---|---|
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ID=39565720
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104007231A (en) * | 2014-05-12 | 2014-08-27 | 青岛农业大学 | Determination method and determination apparatus for virulence of pesticide to corn borer |
| CN104844545A (en) * | 2015-04-07 | 2015-08-19 | 王青虎 | Flavonoid compound and extraction method thereof |
| CN115778935A (en) * | 2022-10-28 | 2023-03-14 | 中山大学 | Application of melinamide in preparation of medicine for preventing and/or treating porcine reproductive and respiratory syndrome |
-
2006
- 2006-12-20 CN CNA2006101654520A patent/CN101205222A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104007231A (en) * | 2014-05-12 | 2014-08-27 | 青岛农业大学 | Determination method and determination apparatus for virulence of pesticide to corn borer |
| CN104844545A (en) * | 2015-04-07 | 2015-08-19 | 王青虎 | Flavonoid compound and extraction method thereof |
| CN115778935A (en) * | 2022-10-28 | 2023-03-14 | 中山大学 | Application of melinamide in preparation of medicine for preventing and/or treating porcine reproductive and respiratory syndrome |
| CN115778935B (en) * | 2022-10-28 | 2024-04-26 | 中山大学 | Application of chinaberry amide in preparation of medicines for preventing and/or treating blue-ear disease |
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