CN101497618B - 4'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate, ether derivative and use in plant source pesticide preparation - Google Patents
4'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate, ether derivative and use in plant source pesticide preparation Download PDFInfo
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Abstract
The invention relates to a series of novel 4'-nordeoxypodophyllotoxin aromatic acid esters, substituted benzene sulfonates, and ether derivatives and application thereof in preparing a botanical insecticide. The 4'-nordeoxypodophyllotoxin aromatic acid esters, the substituted benzene sulfonates, and the ether derivatives have a general chemical formula shown at the right. An experiment proves that the 4'-nordeoxypodophyllotoxin aromatic acid esters, the substituted benzene sulfonates, and the ether derivatives are partially higher than podophyllotoxin and deoxypodophyllotoxin, wherein insecticidal activities of certain compounds are all higher than that of a botanical insecticide-toosendanin which has come into the market, and the compounds can be used for preparing the botanical insecticides with high-efficiency and low-toxicity.
Description
Technical field
The present invention relates to series and have 4 ' of insecticidal activity-remove first deoxidation podophyllotoxin analogue, relate in particular to the application in the preparation plant insecticide of 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative and this 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative.
Background technology
The deoxidation podophyllotoxin is the plant secondary substance that extraction separation comes out from the sandy ground cypress, receives much concern because of having anti-tumor activity.In recent years, it is found that it is to the multiple agriculture and forestry injurious insect restraining effect that has food refusal, kills and grow.
Antitumor and the insecticidal activity of deoxidation podophyllotoxin and derivative has bibliographical information, as: document [Young-Jae You, Yong Kim, Nguyen-Hai Nam, Byung-Zun Ahn.Antitumor activity of unsaturated fattyacid esters of 4 '-demethyldeoxypodophyllotoxin[J] .Bioorganic ﹠amp; MedicinalChemistry Letters.2003,13:2629-2632.] and [Young-Jae You, Yong Kim, Nguyen-HaiNam, Byung-Zun Ahn, et al.Alkyl and carboxylalkyl esters of 4 '-demethyl-4-deoxypodophyllotoxin:synthesis, cytotoxic, and antitumoractivity[J] .European Journal of Medicinal Chemistry.2004,39:189-193.] reported 4 '-go first deoxidation podophyllotoxin and derivative unsaturated and that the saturated fatty acid-respons is prepared to have the good in-vitro anti-tumor activity; Document [Zhang Shougang, Hou Huamin, high Rong. the deoxidation podophyllotoxin is to the influence [J] of the virulence of periplaneta americana and several enzyme system. insect journal, 2007,50 (3): 248-252.] reported that the deoxidation podophyllotoxin just incubates nymph to periplaneta americana and have stronger cytotoxicity; Document [Ma Zhiqing, Feng Juntao, Zhang Xing, podophyllotoxin and deoxidation podophyllotoxin are to mythimna separata biological activity preliminary study [J]. northwest agricultural journal, 2005,14 (1): 94-97.] report deoxidation podophyllotoxin has very strong antifeedant activity to mythimna separata, and it is grown also has restraining effect simultaneously, causing grows respectively goes through the phase and all postpones, and percentage of pupation, eclosion rate, egg laying amount etc. all obviously reduce.But the research synthetic and aspect insecticidal activity of 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative yet there are no report.
Summary of the invention
The objective of the invention is to, provide series new 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative, and provided the preparation method of derivative.According to experiment showed, that 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative have the insecticidal activity of high-efficiency low-toxicity, can be used in the preparation plant insecticide.
For realizing above-mentioned task, the present invention is achieved by following technical measures:
4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative that series is new, its chemical general formula is:
Described 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative, wherein the C-2 position is the α configuration, C-4 ' bit substituent R is:
Described 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative, wherein the C-2 position is the α configuration, C-4 ' bit substituent R is:
Described 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative, wherein the C-2 position of compound 25,27 is the α configuration, and the C-2 position of compound 26,28 is a beta comfiguration, and C-4 ' bit substituent R is:
The preparation method of above-mentioned 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative comprises: the preparation of a, 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester analog derivative 1-16:
With a certain amount of 4 '-go first deoxidation podophyllotoxin, aromatic acid and an amount of 4-Dimethylamino pyridine to be dissolved in the dichloromethane solvent, at room temperature add an amount of dewatering agent N after the stirred for several minute, N '-sec.-propyl carbodiimide places ice-water bath with reaction then.TLC follows the tracks of detection, and reaction finishes after-filtration, removes di-isopropyl urea solid.Use dichloromethane extraction after adding less water in the filtrate, uses anhydrous sodium sulfate drying after merging organic phase, behind the concentrated evaporate to dryness with the preparation silica gel thin sheet separate required pure product.
B, 4 '-the go preparation of first deoxidation podophyllotoxin substituted benzenesulfonic acid ester derivative 17-24:
Toward a certain amount of 4 '-go to add an amount of triethylamine in the dichloromethane solution of first deoxidation podophyllotoxin.Under ice-water bath, slowly drip the substituted benzene SULPHURYL CHLORIDE, dropwise afterreaction and place room temperature.TLC follows the tracks of detection, adds an amount of water stirred for several minute when reaction finishes, and dichloromethane extraction merges after the organic phase with the saturated brine washing, anhydrous sodium sulfate drying, concentrate behind the evaporate to dryness with the preparation silica gel thin sheet separate required pure product.
C, 4 '-the go preparation of first deoxidation podophyllotoxin ether derivative 25-28:
1. 4 '-go the preparation of first deoxidation podophyllotoxin ether derivative 25:
Toward a certain amount of 4 '-go in the acetone soln of first deoxidation podophyllotoxin, salt of wormwood and potassiumiodide, reflux after adding an amount of Benzyl Chloride, TLC follows the tracks of detection, reaction finishes back evaporate to dryness reaction solution, add less water, the water dichloromethane extraction use anhydrous sodium sulfate drying after merging organic phase, behind the concentrated evaporate to dryness with the preparation silica gel thin sheet separate required pure product;
2. 4 '-go the preparation of first deoxidation podophyllotoxin ether derivative 26,27 and 28:
With a certain amount of 4 '-go the acetone soln of first deoxidation podophyllotoxin, methanesulfonates and salt of wormwood to reflux, TLC follows the tracks of detection, reaction finishes back evaporate to dryness reaction solution, add less water, the water dichloromethane extraction, use anhydrous sodium sulfate drying after merging organic phase, behind the concentrated evaporate to dryness with the preparation silica gel thin sheet separate required pure product.
Described 4 '-as to go the preparation method of first deoxidation podophyllotoxin:
The liquid bromine is slowly splashed in the naphthane solution that is mixed with a small amount of iron powder, the bromize hydrogen gas that produces feeds in the dark cold-trap after passing through the wash bottle that fills naphthane solution, the hydrogen bromide feeding of overflowing from cold-trap contains 1 of deoxidation podophyllotoxin and ether, in the 2-dichloroethane solution, stirring reaction under ice-water bath.TLC follows the tracks of detection, and reaction adds an amount of equal proportion when complete substantially water and acetone soln and a little barium carbonate stirred 30 minutes.The reaction solution ethyl acetate extraction, organic phase is washed with saturated brine, anhydrous sodium sulfate drying, concentrate evaporate to dryness after silica gel column chromatography separate required pure product.
The preparation method of above-mentioned deoxidation podophyllotoxin:
With a certain amount of podophyllotoxin and a small amount of 10% palladium carbon with the Glacial acetic acid dissolving after, under 2 normal atmosphere, 95 ℃ condition, in autoclave, reacted 5 hours with hydrogen.After reaction finished, filtering reacting liquid was removed palladium carbon.Filtrate decompression distillation, solvent evaporated after silica gel column chromatography separate crude product, get required pure product through recrystallizing methanol again.
The preparation method of described 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative, wherein used aromatic acid, substituted benzene SULPHURYL CHLORIDE, methanesulfonates are respectively:
A, aromatic acid are: toluylic acid, phenylformic acid, p-methylbenzoic acid, m-methyl benzoic acid, anisic acid, 0-chloro-benzoic acid, m-chlorobenzoic acid, Chlorodracylic acid, naphthylacetic acid, M-NITROBENZOIC ACID, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, styracin, nicotinic acid, 3-indolebutyric acid or Yi Yansuan;
B, substituted benzene SULPHURYL CHLORIDE are: m-nitrobenzene sulfonyl chloride, benzene sulfonyl chloride, to anisole SULPHURYL CHLORIDE, m-chloro p-nitrophenyl SULPHURYL CHLORIDE, parachloroben-zenesulfonyl chloride, p-methyl benzene sulfonic chloride, to ethylbenzene SULPHURYL CHLORIDE or p-bromobenzenesulfonyl chloride;
C, methanesulfonate ester are: methylsulfonic acid to methoxy benzyl ester or methylsulfonic acid to the nitrobenzyl ester.
Experimental results show that, 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester of the present invention, substituted benzene sulfonate and ether derivative have the food refusal cytotoxicity to the agriculture and forestry injurious insect mythimna separata, and the activity of part of compounds is higher than the botanical pesticide Toosendanin that has now gone on the market, can be used for preparing good plant insecticide.
Description of drawings
Fig. 1, Fig. 2, Fig. 3, the mass spectrum that is respectively compound 1, hydrogen spectrum and infared spectrum;
Fig. 4, Fig. 5, Fig. 6, the mass spectrum that is respectively compound 20, hydrogen spectrum and infared spectrum;
Fig. 7, Fig. 8, Fig. 9, the mass spectrum that is respectively compound 25, hydrogen spectrum and infared spectrum.
Below the embodiment that provides by accompanying drawing and contriver the present invention done further elaborate.
Embodiment
The present invention is according to the similarity and 4 ' of organism biological effect-the go anti-tumor activity result of study of first deoxidation podophyllotoxin fatty acid ester analog derivative, synthesize serial new 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative, and carried out insecticidal activity research.The result shows that 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester of the present invention, substituted benzene sulfonate and ether derivative have stronger food refusal cytotoxicity to the agriculture and forestry injurious insect mythimna separata, can be used for preparing the plant insecticide of high-efficiency low-toxicity.
Embodiment 1:
One, product: deoxidation podophyllotoxin, 4 '-go first deoxidation podophyllotoxin and compound 1-28 (each compound physico-chemical property sees following content for details)
Two, preparation method:
Below for the synthetic route of deoxidation podophyllotoxin:
With 16g podophyllotoxin and 12g10% palladium carbon with 150 milliliters of Glacial acetic acid dissolvings after, under 2 normal atmosphere, 95 ℃ condition, in autoclave, reacted 5 hours with hydrogen.Reaction finishes the after-filtration reaction solution, removes palladium carbon, filtrate after the underpressure distillation solvent evaporated, through silica gel column chromatography separate crude product, get required pure product through recrystallizing methanol.
Podophyllotoxin deoxidation podophyllotoxin
The physico-chemical property of deoxidation podophyllotoxin is as follows:
1), white solid, fusing point 165-167 ℃, specific rotatory power [α]
20 D=-116 ° (C=10mg/mL, chloroform);
2), the infrared spectrogram of deoxidation podophyllotoxin (IR) feature:
Adopt pellet technique: 1763cm
-1Be lactonic ring carbonyl absorption, 1587,1482,1457cm
-1Be aromatic ring frame absorption of vibrations, 1223,1120cm
-1For (C-O-C) absorbs, 925cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of deoxidation podophyllotoxin (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 6.67 (s, 1H, H-5), 6.52 (s, 1H, H-8), 6.34 (s, 2H, H-2 ', 6 '), 5.93 (d, J=8.0Hz, 2H, OCH
2O), 4.60 (s, 1H, H-1), 4.43 (m, 1H, H-11), 3.89 (m, 1H, H-11), 3.79 (s, 3H, 4 '-OCH
3), 3.75 (s, 6H, 3 ', 5 '-OCH
3), 3.06 (m, 1H, H-4), 2.71 (m, 3H, H-2,3,4).
4), EI source mass spectrum (MS) the figure feature of deoxidation podophyllotoxin: its molecular ion peak is 398.1.
Below be 4 '-go the synthetic route of first deoxidation podophyllotoxin:
The liquid bromine is slowly splashed in the 30ml naphthane solution that is mixed with a small amount of iron powder, feed in the dark cold-trap after the wash bottle of bromize hydrogen gas that produces through filling naphthane solution, the hydrogen bromide feeding of overflowing from cold-trap contains 1 of 2g deoxidation podophyllotoxin and 2.5ml ether, in 2-ethylene dichloride (25ml) solution, stirring reaction under the ice-water bath.TLC follows the tracks of detection, and reaction adds 25ml when complete substantially water and acetone (1: 1) solution and a little barium carbonate stirred 30 minutes.Reaction solution with ethyl acetate (4 * 30ml) extractions, merge after the organic phase with saturated brine (2 * 50ml) washings, anhydrous sodium sulfate drying, concentrated evaporate to dryness after silica gel column chromatography separate required pure product.
Deoxidation podophyllotoxin 4 '-go first deoxidation podophyllotoxin
4 '-go the physico-chemical property of first deoxidation podophyllotoxin as follows:
1), white solid, fusing point 246-248 ℃, specific rotatory power [α]
20 D=-130 ° (C=4mg/mL, chloroform);
2), 4 '-go infrared spectrogram (IR) feature of first deoxidation podophyllotoxin:
Adopt pellet technique: 3384cm
-1Be phenolic hydroxyl group stretching vibration, 1757cm
-1Be lactonic ring carbonyl absorption, 1608,1478,1458cm
-1Be aromatic ring frame absorption of vibrations, 1214,1105cm
-1For (C-O-C) absorbs, 922cm
-1Be (OCH
2O-) absorb.
3), 4 '-go first deoxidation podophyllotoxin nuclear magnetic resonance map (
1HNMR, 400MHz) feature: with the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 6.66 (s, 1H, H-5), 6.51 (s, 1H, H-8), 6.35 (s, 2H, H-2 ', 6 '), 5.92 (m, 2H, OCH
2O), 5.39 (s, 1H, 4 '-OH), 4.59 (d, J=2.4Hz, 1H, H-1), 4.42 (m, 1H, H-11), 3.88 (m, 1H, H-11), 3.78 (s, 6H, 3 ', 5 '-OCH
3), 3.05 (m, 1H, H-4), 2.71 (m, 3H, H-2,3,4).
4), 4 '-and going EI source mass spectrum (MS) the figure feature of first deoxidation podophyllotoxin: its molecular ion peak is 383.9.
Below be the synthetic route of compound 1-16:
With 0.25mmol4 '-go first deoxidation podophyllotoxin, 0.3mmol aromatic acid and 0.1mmol 4-Dimethylamino pyridine to be dissolved in the 10ml exsiccant dichloromethane solvent, behind stirring at room number minute, add 0.3mmol dewatering agent N, N '-sec.-propyl carbodiimide, then reaction is placed ice-water bath, TLC follows the tracks of detection, reaction finishes after-filtration, removes di-isopropyl urea solid.Add 25ml water in the filtrate, with methylene dichloride (4 * 30ml) extractions use anhydrous sodium sulfate drying after merging organic phase, behind the concentrated evaporate to dryness with the preparation silica gel thin sheet separate required pure product.
Reaction expression is as follows:
Below said compound 1～16, be meant the abbreviation of 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester analog derivative, compound 17～24, be meant 4 '-go the abbreviation of first deoxidation podophyllotoxin substituted benzenesulfonic acid ester derivative, compound 26～28 to be meant 4 '-to remove the abbreviation of first deoxidation podophyllotoxin ether derivative.
Compound 1:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 223-225 ℃, specific rotatory power [α]
20 D=-79 ° (C=2.9mg/mL, chloroform);
2), infrared spectrogram (IR) feature of this compound (1):
Adopt pellet technique: 1779cm
-1Be lactonic ring carbonyl absorption, 1759cm
-1Be the carbonyl absorption of toluylic acid, 1597,1482,1459cm
-1Be aromatic ring frame absorption of vibrations, 1224,1122cm
-1For (C-O-C) absorbs, 928cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.38 (d, J=7.2Hz, 2H, H-2 ", 6 "), 7.32 (m, 2H, H-3 "; 5 "), 7.28 (d, J=7.6Hz, 1H, H-4 "); 6.65 (s, 1H, H-5), 6.51 (s, 1H; H-8), 6.35 (s, 2H, H-2 ', 6 '); 5.92 (dd, J=1.2Hz, J=8.0Hz, 2H, OCH
2O), 4.61 (d, J=4.4Hz, 1H, H-1), 4.42 (m, 1H, H-11), 3.88 (m, 3H, H-11and
CH 2 C
6H
5), 3.62 (s, 6H, 3 ', 5 '-OCH
3), 3.03 (m, 1H, H-4), 2.69 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 525.
5), reaction formula is:
Compound 2:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 256-258 ℃, specific rotatory power [α]
20 D=-80 ° (C=2.6mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1761cm
-1Be lactonic ring carbonyl absorption, 1738cm
-1Be benzoic carbonyl absorption, 1597,1486,1454cm
-1Be aromatic ring frame absorption of vibrations, 1230,1128cm
-1For (C-O-C) absorbs, 928cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.19 (d, J=7.6Hz, 2H, H-2 ", 6 "), 7.59 (t, J=7.6Hz, 1H, H-4 "), 7.46 (t, J=7.6Hz, 2H, H-3 ", 5 "), 6.68 (s, 1H, H-5), 6.59 (s; 1H, H-8), 6.43 (s, 2H, H-2 '; 6 '), 5.94 (d, J=7.6Hz, 2H, OCH
2O), 4.67 (s, 1H, H-1), 4.46 (m, 1H, H-11), 3.89 (m, 1H, H-11), 3.69 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.76 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 511.
5) reaction formula is:
Compound 3:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 246-247 ℃, specific rotatory power [α]
20 D=-74 ° (C=3mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1761cm
-1Be lactonic ring carbonyl absorption, 1736cm
-1Be the carbonyl absorption of p-methylbenzoic acid, 1597,1486,1458cm
-1Be aromatic ring frame absorption of vibrations, 1229,1129cm
-1For (C-O-C) absorbs, 927cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.08 (d, J=8.0Hz, 2H, H-2 ", 6 "), 7.27 (d, J=7.6Hz, 2H, H-3 ", 5 "), 6.67 (s, 1H, H-5), 6.56 (s, 1H, H-8), 6.42 (s, 2H, H-2 ', 6 '), 5.94 (d, J=7.2Hz, 2H, OCH
2O), 4.67 (s, 1H, H-1), 4.46 (m, 1H, H-11), 3.88 (m, 1H, H-11), 3.68 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.76 (m, 3H, H-2,3,4), 2.43 (s, 3H, C
6H
4 CH 3 ).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 525.
5), reaction formula is:
Compound 4:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 253-254 ℃, specific rotatory power [α]
20 D=-76 ° (C=2.2mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1762cm
-1Be lactonic ring carbonyl absorption, 1734cm
-1Be the carbonyl absorption of m-methyl benzoic acid, 1596,1485,1459cm
-1Be aromatic ring frame absorption of vibrations, 1229,1128cm
-1For (C-O-C) absorbs, 927cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.01 (s, 1H, H-2 "); 7.99 (d, J=8.8Hz, 1H, H-6 "), 7.35 (m, 2H, H-4 ", 5 "), 6.67 (s, 1H, H-5), 6.56 (s, 1H, H-8), 6.42 (s, 2H, H-2 ', 6 '), 5.94 (dd, J=1.2Hz, J=8.4Hz, 2H, OCH
2O), 4.66 (d, J=3.2Hz, 1H, H-1), 4.46 (m, 1H, H-11), 3.91 (m, 1H, H-11), 3.69 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.76 (m, 3H, H-2,3,4), 2.42 (s, 3H, C
6H
4 CH 3 ).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 525.
5), reaction formula is:
Compound 5:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 263-265 ℃, specific rotatory power [α]
20 D=-76 ° (C=3.2mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1762cm
-1Be lactonic ring carbonyl absorption, 1731cm
-1Be the carbonyl absorption of anisic acid, 1598,1485,1460cm
-1Be aromatic ring frame absorption of vibrations, 1227,1130cm
-1For (C-O-C) absorbs, 925cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.14 (d, J=8.8Hz, 2H, H-2 ", 6 "), 6.95 (d, J=8.4Hz, 2H, H-3 ", 5 "), 6.67 (s, 1H, H-5), 6.56 (s, 1H, H-8), 6.42 (s, 2H, H-2 ', 6 '), 5.94 (m, 2H, OCH
2O), 4.67 (s, 1H, H-1), 4.46 (m, 1H, H-11), 3.91 (m, 1H, H-11), 3.88 (s, 3H, C
6H
4O
CH 3 ), 3.68 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.76 (m, 3H, H-2,3,4);
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 541.
5), reaction formula is:
Compound 6:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 236-237 ℃, specific rotatory power [α]
20 D=-75 ° (C=3.4mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1761cm
-1Be lactonic ring carbonyl absorption, 1736cm
-1Be the carbonyl absorption of 0-chloro-benzoic acid, 1598,1485,1457cm
-1Be aromatic ring frame absorption of vibrations, 1228,1129cm
-1For (C-O-C) absorbs, 924cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.10 (dd, J=1.6Hz, J=7.6Hz, 1H, H-6 "), 7.46 (m, 2H, H-4 ", 5 "), 7.34 (m, 1H, H-3 "), 6.68 (s, 1H, H-5), 6.55 (s, 1H, H-8), 6.43 (s, 2H, H-2 ', 6 '), 5.94 (dd, J=1.2Hz, J=8.0Hz, 2H, OCH
2O), 4.66 (d, J=3.6Hz, 1H, H-1), 4.46 (m, 1H, H-11), 3.91 (m, 1H, H-11), 3.72 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.76 (m, 128,3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 545.
5), reaction formula is:
Compound 7:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 247-249 ℃, specific rotatory power [α]
20 D=-73 ° (C=3.6mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1762cm
-1Be lactonic ring carbonyl absorption, 1741cm
-1Be the carbonyl absorption of m-chlorobenzoic acid, 1597,1487,1459cm
-1Be aromatic ring frame absorption of vibrations, 1230,1127cm
-1For (C-O-C) absorbs, 928cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.18 (s, 1H, H-2 "), 8.07 (d; J=8Hz, 1H, H-6 "), 7.51 (d, J=8Hz, 1H, H-4 "), 7.43 (t, J=8Hz, 1H; H-5 "), 6.68 (s, 1H, H-5), 6.56 (s, 1H, H-8), 6.43 (s, 2H, H-2 ', 6 '), 5.94 (d, J=8.4Hz, 2H, OCH
2O), 4.67 (s, 1H, H-1), 4.48 (m, 1H, H-11), 3.92 (m, 1H, H-11), 3.69 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4); (2.76 m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 545.
5), reaction formula is:
Compound 8:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 246-248 ℃, specific rotatory power [α]
20 D=-71 ° (C=2.1mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1762cm
-1Be lactonic ring carbonyl absorption, 1740cm
-1Be the carbonyl absorption of Chlorodracylic acid, 1597,1485,1462cm
-1Be aromatic ring frame absorption of vibrations, 1229,1129cm
-1For (C-O-C) absorbs, 928cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.12 (d, J=8.8Hz, 2H, H-2 ", 6 "), 7.44 (d, J=8.4Hz, 2H, H-3 ", 5 "), 6.67 (s, 1H, H-5), 6.55 (s, 1H, H-8), 6.42 (s, 2H, H-2 ', 6 '), 5.94 (m, 2H, OCH
2O), 4.66 (d, J=3.6Hz, 1H, H-1), 4.46 (m, 1H, H-11), 3.91 (m, 1H, H-11), 3.68 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.76 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 545.
5), reaction formula is:
Compound 9:
The physico-chemical property of this compound is as follows:
1), white solid, 196 ℃ of fusing points, specific rotatory power [α]
20 D=-65 ° (C=3.5mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1761cm
-1Be lactonic ring carbonyl absorption, 1597,1484,1459cm
-1Be aromatic ring frame absorption of vibrations, 1227,1120cm
-1For (C-O-C) absorbs, 928cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.12 (d, J=8.8Hz, 1H, H-8 "); 7.85 (d, J=7.2Hz, 1H, H-5 "), 7.78 (d, J=8.0Hz, 1H, H-4 "), 7.41 (m, 4H, H-2 ", 3 "; 6 ", 7 "), 6.64 (s, 1H, H-5), 6.48 (s; 1H, H-8), 6.31 (s, 2H, H-2 '; 6 '), 5.91 (d, J=5.6Hz, 2H, OCH
2O), 4.59 (d, J=4.0Hz, 1H, H-1), 4.39 (m, 1H, H-11), 4.33 (s, 2H,
CH 2 C
10H
8), 3.86 (m, 1H, H-11), 3.55 (s, 6H, 3 ', 5 '-OCH
3), 3.01 (m, 1H, H-4), 2.69 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 575.
5), reaction formula is:
Compound 10:
The physico-chemical property of this compound is as follows:
1), yellow solid, fusing point 137-138 ℃, specific rotatory power [α]
20 D=-72 ° (C=2.9mg/mL chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1746cm
-1Be the carbonyl absorption of M-NITROBENZOIC ACID, 1600,1482,1459cm
-1Be aromatic ring frame absorption of vibrations, 1225,1125cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 9.03 (s, 1H, H-2 "), 8.50 (dd; J=1.2Hz, J=8.0Hz, 1H, H-6 "), 8.45 (m, 1H, H-4 "), 7.68 (t, J=7.6Hz, 1H; H-5 "), 6.68 (s, 1H, H-5), 6.56 (s, 1H, H-8), 6.44 (s, 2H, H-2 ', 6 '), 5.95 (d, J=8.8Hz, 2H, OCH
2O), 4.67 (d, J=3.2Hz, 1H, H-1), 4.47 (m, 1H, H-11), 3.93 (m, 1H, H-11), 3.70 (s, 6H, 3 ', 5 '-OCH
3), 3.08 (m, 1H, H-4), 2.77 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 556.
5) reaction formula is:
Compound 11:
The physico-chemical property of this compound is as follows:
1), yellow solid, fusing point 133-134 ℃, specific rotatory power [α]
20 D=-63 ° (C=4.8mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1771cm
-1Be lactonic ring carbonyl absorption, 1743cm
-1Be the carbonyl absorption of p-nitrobenzoic acid, 1600,1482,1461cm
-1Be aromatic ring frame absorption of vibrations, 1225,1126cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.35 (dd, J=2.0Hz, J=6.8Hz, 2H, H-3 ", 5 "), 8.31 (dd, J=2.0Hz, J=6.8Hz, 2H, H-2 ", 6 "), 6.68 (s, 1H, H-5), 6.55 (s, 1H, H-8), 6.44 (s, 2H, H-2 ', 6 '), 5.94 (dd, J=1.2Hz, J=8.4Hz, 2H, OCH
2O), 4.67 (d, J=4Hz, 1H, H-1), 4.46 (m, 1H, H-11), 3.92 (m, 1H, H-11), 3.69 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.73 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 556.
5), reaction formula is:
Compound 12:
The physico-chemical property of this compound is as follows:
1), yellow solid, fusing point 272-274 ℃, specific rotatory power [α]
20 D=-73 ° (C=2.9mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1753cm
-1Be 3, the carbonyl absorption of 5-dinitrobenzoic acid, 1600,1485,1460cm
-1Be aromatic ring frame absorption of vibrations, 1227,1133cm
-1For (C-O-C) absorbs, 924cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 9.30 (d, J=2.0Hz, 2H, H-2 ", 6 "), 9.26 (t, J=2.0Hz, 1H, H-4 "), 6.69 (s, 1H, H-5); 6.56 (s, 1H, H-8), 6.46 (s; 2H, H-2 ', 6 '), 5.94 (dd; J=0.8Hz, J=9.2Hz, 2H, OCH
2O), 4.68 (d, J=4Hz, 1H, H-1), 4.48 (m, 1H, H-11), 3.93 (m, 1H, H-11), 3.70 (s, 6H, 3 ', 5 '-OCH
3), 3.09 (m, 1H, H-4), 2.74 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 556.
5), reaction formula is:
Compound 13:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 142-144 ℃, specific rotatory power [α]
20 D=-81 ° (C=1.9mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1761cm
-1Be lactonic ring carbonyl absorption, 1735cm
-1Be the carbonyl absorption of styracin, 1595,1486,1454cm
-1Be aromatic ring frame absorption of vibrations, 1228,1123cm
-1For (C-O-C) absorbs, 925cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.83 (d, J=16.0Hz, 1H ,-CH=
CH-C
6H
5), 7.56 (m, 2H, H-3 ", 5 "), 7.39 (m, 3H, H-2 ", 4 ", 6 "), 6.67 (d, J=16.0Hz, 1H ,-
CH=CH-C
6H
5), 6.67 (s, 1H, H-5), 6.55 (s, 1H, H-8), 6.41 (s, 2H, H-2 ', 6 '), 5.93 (d, J=8.4Hz, 2H, OCH
2O), 4.66 (s, 1H, H-1), 4.46 (m, 1H, H-11), 3.90 (m, 1H, H-11), 3.71 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.75 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 537.
5), reaction formula is:
Compound 14:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 259-260 ℃, specific rotatory power [α]
20 D=-73 ° (C=4.3mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1761cm
-1Be lactonic ring carbonyl absorption, 1741cm
-1Be the carbonyl absorption of nicotinic acid, 1595,1485,1455cm
-1Be aromatic ring frame absorption of vibrations, 1228,1125cm
-1For (C-O-C) absorbs, 928cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 9.38 (s, 1H, H-2 "); 8.82 (d, J=3.6Hz, 1H, H-6 "), 8.42 (m, 1H, H-4 "), 7.41 (m, 1H, H-5 "), 6.68 (s, 1H, H-5), 6.55 (s, 1H, H-8), 6.44 (s, 2H, H-2 ', 6 '), 5.94 (m, 2H, OCH
2O), 4.66 (d, J=3.6Hz, 1H, H-1), 4.46 (m, 1H, H-11), 3.88 (m, 1H, H-11), 3.69 (s, 6H, 3 ', 5 '-OCH
3), 3.06 (m, 1H, H-4), 2.73 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 512.
5), reaction formula is:
Compound 15:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 106-107 ℃, specific rotatory power [α]
20 D=-68 ° (C=4.5mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1759cm
-1Be the carbonyl absorption of 3-indolebutyric acid, 1598,1482,1457cm
-1Be aromatic ring frame absorption of vibrations, 1224,1124cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.94 (s, 1H, NH), 7.63 (d, J=8.0Hz, 1H, H-4 "), 7.34 (d, J=8.0Hz, 1H, H-7 "), 7.16 (t, J=7.2Hz, 1H, H-6 "), 7.08 (t, J=7.2Hz, 1H, H-5 "), 7.03 (d, J=2.0Hz, 1H, H-2 "), 6.66 (s, 1H, H-5); 6.53 (s, 1H, H-8), 6.38 (s, 2H, H-2 '; 6 '), 5.92 (dd, J=0.8Hz, J=7.6Hz, 2H, OCH
2O), 4.63 (d, J=3.6Hz, 1H, H-1), 4.43 (m, 1H, H-11), 3.89 (m, 1H, H-11), 3.68 (s, 6H, 3 ', 5 '-OCH
3), 3.04 (m, 1H, H-4), 2.89 (t, J=7.2Hz, 2H,
CH 2 (CH
2)
2-indole), 2.71 (m, 3H, H-2,3,4), 2.63 (t, J=7.2Hz, 2H, (CH
2)
2 CH 2 -indole), 2.11 (m, 2H, CH
2 CH 2 CH
2-indole).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 592.
5), reaction formula is:
Compound 16:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 208-210 ℃, specific rotatory power [α]
20 D=-84 ° (C=2.4mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1762cm
-1Be lactonic ring carbonyl absorption, 1745cm
-1Be the carbonyl absorption of Yi Yansuan, 1600,1485,1463cm
-1Be aromatic ring frame absorption of vibrations, 1227,1132cm
-1For (C-O-C) absorbs, 927cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.82 (d, J=5.6Hz, 2H, H-2 ", 6 "), 7.99 (dd, J=1.6Hz, J=4.8Hz, 2H, H-3 ", 5 "), 6.68 (s, 1H, H-5), 6.55 (s, 1H, H-8), 6.43 (s, 2H, H-2 ', 6 '), 5.94 (dd, J=1.2Hz, J=8.0Hz, 2H, OCH
2O), 4.66 (d, J=4Hz, 1H, H-1), 4.47 (m, 1H, H-11), 3.88 (m, 1H, H-11), 3.69 (s, 6H, 3 ', 5 '-OCH
3), 3.07 (m, 1H, H-4), 2.72 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 512.
5), reaction formula is:
Below be the synthetic route of compound 17-24:
With 0.2mmol4 '-go first deoxidation podophyllotoxin to be dissolved in the 10ml exsiccant dichloromethane solution, add the 0.6mmol triethylamine again.Under ice-water bath, slowly drip substituted benzene SULPHURYL CHLORIDE (0.24mmol), dropwise afterreaction and place room temperature.TLC follows the tracks of detection, adds an amount of water stirred for several minute after reaction finishes.Methylene dichloride (4 * 20ml) extractions, merge after the organic phase with saturated brine (2 * 50ml) washings, anhydrous sodium sulfate drying, concentrate behind the evaporate to dryness with the preparation silica gel thin sheet separate required pure product.
Reaction expression is as follows:
Compound 17:
The physico-chemical property of this compound is as follows:
1), yellow solid, 115 ℃ of fusing points, specific rotatory power [α]
20 D=-48 ° (C=4mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1769cm
-1Be lactonic ring carbonyl absorption, 1598,1483,1462cm
-1Be aromatic ring frame absorption of vibrations 1378cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs, 1225,1126cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.89 (s, 1H, H-2 "); 8.48 (m, 1H, H-6 "), 8.30 (m, 1H, H-4 "), 7.74 (t, J=8Hz, 1H, H-5 "), 6.67 (s, 1H, H-5), 6.50 (s, 1H, H-8), 6.36 (s, 2H, H-2 ', 6 '), 5.94 (dd, J=1.2Hz, J=10Hz, 2H, OCH
2O), 4.61 (d, J=4.8Hz, 1H, H-1), 4.46 (m, 1H, H-11), 3.90 (m, 1H, H-11), 3.61 (s, 6H, 3 ', 5 '-OCH
3), 3.05 (m, 1H, H-4), 2.74 (m, 3H, H-2,3,4).
4), reaction formula is:
Compound 18:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 248-250 ℃, specific rotatory power [α]
20 D=-70 ° (C=5.3mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1765cm
-1Be lactonic ring carbonyl absorption, 1596,1484,1460cm
-1Be aromatic ring frame absorption of vibrations 1373cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs, 1227,1129cm
-1For (C-O-C) absorbs, 932cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.95 (d, J=8.8Hz, 2H, H-2 "; 6 "), 7.61 (t, J=8Hz, 1H, H-4 "); 7.50 (t, J=8Hz, 2H, H-3 ", 5 "); 6.66 (s, 1H, H-5), 6.50 (s, 1H; H-8), 6.32 (s, 2H, H-2 ', 6 '); 5.93 (dd, J=1.2Hz, J=9.6Hz, 2H, OCH
2O), 4.59 (d, J=4.8Hz, 1H, H-1), 4.45 (m, 1H, H-11), 3.90 (m, 1H, H-11), 3.53 (s, 6H, 3 ', 5 '-OCH
3), 3.04 (m, 1H, H-4), 2.68 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+1]
+The peak is 525.
5), reaction formula is:
Compound 19:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 94-96 ℃, specific rotatory power [α]
20 D=-47 ° (C=3.6mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1767cm
-1Be lactonic ring carbonyl absorption, 1595,1483,1460cm
-1Be aromatic ring frame absorption of vibrations 1367cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs,, 1225,1127cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.87 (d, J=8.8Hz, 2H, H-2 ", 6 "), 6.96 (d, J=8.8Hz, 2H, H-3 ", 5 "), 6.66 (s, 1H, H-5), 6.50 (s, 1H, H-8), 6.32 (s, 2H, H-2 ', 6 '), 5.93 (s, 2H, OCH
2O), 4.59 (d, J=4Hz, 1H, H-1), 4.45 (m, 1H, H-11), 3.88 (m, 1H, H-11), 3.88 (s, 3H, C
6H
4O
CH 3 ), 3.57 (s, 6H, 3 ', 5 '-OCH
3), 3.04 (m, 1H, H-4), 2.72 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+1]
+The peak is 555.
5), reaction formula is:
Compound 20:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 97-99 ℃, specific rotatory power [α]
20 D=-58 ° (C=7mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1769cm
-1Be lactonic ring carbonyl absorption, 1597,1483,1462cm
-1Be aromatic ring frame absorption of vibrations 1379cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs, 1225,1127cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.48 (d, J=2.4Hz, 1H, H-2 "), 8.09 (dd, J=2Hz, J=8.4Hz, 1H; H-5 "), 7.73 (d, J=8.8Hz, 1H, H-6 "); 6.67 (s, 1H, H-5), 6.50 (s, 1H; H-8), 6.36 (s, 2H, H-2 ', 6 '); 5.94 (dd, J=1.2Hz, J=10Hz, 2H, OCH
2O), 4.61 (d, J=4.8Hz, 1H, H-1), 4.46 (m, 1H, H-11), 3.91 (m, 1H, H-11), 3.62 (s, 6H, 3 ', 5 '-OCH
3), 3.05 (m, 1H, H-4), 2.65 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+1]
+The peak is 604.
5), reaction formula is:
Compound 21:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 114-116 ℃, specific rotatory power [α]
20 D=-57 ° (C=7mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1769cm
-1Be lactonic ring carbonyl absorption, 1597,1482,1461cm
-1Be aromatic ring frame absorption of vibrations 1374cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs, 1225,1127cm
-1For (C-O-C) absorbs, 930cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.88 (d, J=7.2Hz, 2H, H-2 ", 6 "), 7.49 (d, J=8.8Hz, 2H, H-3 ", 5 "), 6.66 (s, 1H, H-5), 6.49 (s, 1H, H-8), 6.33 (s, 2H, H-2 ', 6 '), 5.93 (dd, J=1.2Hz, J=9.6Hz, 2H, OCH
2O), 4.59 (d, J=4.8Hz, 1H, H-1), 4.45 (m, 1H, H-11), 3.90 (m, 1H, H-11), 3.56 (s, 6H, 3 ', 5 '-OCH
3), 3.04 (m, 1H, H-4), 2.65 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+1]
+The peak is 559.
5), reaction formula is:
Compound 22:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 97-99 ℃, specific rotatory power [α]
20 D=-50 ° (C=4.2mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1769cm
-1Be lactonic ring carbonyl absorption, 1596,1483,1460cm
-1Be aromatic ring frame absorption of vibrations 1368cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs, 1225,1127cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.83 (d, J=8.4Hz, 2H, H-2 ", 6 ' '), 7.30 (d, J=8Hz, 2H; H-3 ", 5 "), 6.66 (s, 1H, H-5); 6.50 (s, 1H, H-8), 6.32 (s; 2H, H-2 ', 6 '), 5.93 (dd; J=1.2Hz, J=9.2Hz, 2H, OCH
2O), 4.59 (d, J=4.8Hz, 1H, H-1), 4.45 (m, 1H, H-11), 3.89 (m, 1H, H-11), 3.55 (s, 6H, 3 ', 5 '-OCH
3), 3.04 (m, 1H, H-4), 2.66 (m, 3H, H-2,3,4), 2.45 (s, 3H, C
6H
4 CH 3 ).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+1]
+The peak is 539.
5), reaction formula is:
Compound 23:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 106-107 ℃, specific rotatory power [α]
20 D=-60 ° (C=4.1mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1770cm
-1Be lactonic ring carbonyl absorption, 1596,1483,1460cm
-1Be aromatic ring frame absorption of vibrations 1369cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs, 1225,1127cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.85 (d, J=8.4Hz, 2H, H-2 ", 6 "), 7.33 (d, J=8.4Hz, 2H, H-3 ", 5 "), 6.66 (s, 1H, H-5), 6.50 (s, 1H, H-8), 6.32 (s, 2H, H-2 ', 6 '), 5.93 (dd, J=1.2Hz, J=9.2Hz, 2H, OCH
2O), 4.59 (d, J=4.8Hz, 1H, H-1), 4.45 (m, 1H, H-11), 3.90 (m, 1H, H-11), 3.54 (s, 6H, 3 ', 5 '-OCH
3), 3.04 (m, 1H, H-4), 2.69 (m, 5H, H-2,3,4, C
6H
4 CH 2 CH
3), 1.25 (t, J=7.6Hz, 3H, C
6H
4CH
2 CH 3 ).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+1]
+The peak is 553.
5), reaction formula is:
Compound 24:
The physico-chemical property of this compound is as follows:
1), white solid, fusing point 96-98 ℃, specific rotatory power [α]
20 D=-53 ° (C=3.6mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1769cm
-1Be lactonic ring carbonyl absorption, 1597,1483,1462cm
-1Be aromatic ring frame absorption of vibrations 1373cm
-1For the sulfur-to-oxygen double bond stretching vibration absorbs, 1225,1127cm
-1For (C-O-C) absorbs, 930cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.80 (d, J=8.4Hz, 2H, H-2 ", 6 "), 7.49 (d, J=8.8Hz, 2H, H-3 ", 5 "), 6.66 (s, 1H, H-5), 6.49 (s, 1H, H-8), 6.32 (s, 2H, H-2 ', 6 '), 5.93 (dd, J=1.2Hz, J=9.6Hz, 2H, OCH
2O), 4.59 (d, J=4.8Hz, 1H, H-1), 4.45 (m, 1H, H-11), 3.90 (m, 1H, H-11), 3.56 (s, 6H, 3 ', 5 '-OCH
3), 3.04 (m, 1H, H-4), 2.65 (m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+1]
+The peak is 603.
Reaction formula is:
Compound 25:
Below be the synthetic route of compound 25:
With 4 '-go first deoxidation podophyllotoxin (0.2mmol), salt of wormwood (0.72mmol) and potassiumiodide (0.06mmol) to be dissolved in the 10ml acetone soln after, adding Benzyl Chloride (0.25mmol) back refluxes, TLC follows the tracks of detection, reaction finishes back evaporate to dryness reaction solution, add less water, water with methylene dichloride (2 * 20ml) extractions use anhydrous sodium sulfate drying after merging organic phase, concentrate prepare behind the evaporate to dryness silica gel thin sheet separate required pure product.
The physico-chemical property of this compound is as follows:
1), white solid, 71 ℃ of fusing points, specific rotatory power [α]
20 D=-90 ° (C=4.4mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1767cm
-1Be lactonic ring carbonyl absorption, 1586,1481,1454cm
-1Be aromatic ring frame absorption of vibrations, 1223,1122cm
-1For (C-O-C) absorbs, 929cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.45 (d, J=7.2Hz, 2H, H-2 ", 6 "), 7.26 (m, 3H, H-3 ", 5 ", 4 "), 6.66 (s, 1H, H-5), 6.53 (s, 1H, H-8); 6.32 (s, 2H, H-2 ', 6 '), 5.92 (d, J=8.4Hz, 2H, OCH
2O), 4.95 (s, 2H,
CH 2 C
6H
5), 4.59 (d, J=2.8Hz, 1H, H-1), 4.43 (m, 1H, H-11), 3.89 (m, 1H, H-11), 3.72 (s, 6H, 3 ', 5 '-OCH
3), 3.05 (m, 1H, H-4); (2.68 m, 3H, H-2,3,4).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 497.
5), reaction formula is:
Below be the synthetic route of compound 26-28:
With 4 '-go first deoxidation podophyllotoxin (0.2mmol), methanesulfonates (0.24mmol), salt of wormwood (0.72mmol) to reflux after being dissolved in the 10ml acetone soln, TLC follows the tracks of detection, reaction finishes back evaporate to dryness reaction solution, add less water, (2 * 20ml) extract water with methylene dichloride, use anhydrous sodium sulfate drying after merging organic phase, behind the concentrated evaporate to dryness with the preparation silica gel thin sheet separate required pure product.
Reaction expression is as follows:
Compound 26:
The physico-chemical property of this compound is as follows:
1), white solid, 110 ℃ of fusing points, specific rotatory power [α]
20 D=+19 ° (C=4.7mg/mL, chloroform);
2), the infrared spectrogram of this compound (IR) feature:
Adopt pellet technique: 1762cm
-1Be lactonic ring carbonyl absorption, 1588,1479,1462cm
-1Be aromatic ring frame absorption of vibrations, 1242,1123cm
-1For (C-O-C) absorbs, 923cm
-1Be (OCH
2O-) absorb.
3), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 7.37 (d, J=8.8Hz, 2H, H-2 ", 6 "), 6.85 (d, J=8.4Hz, 2H, H-3 ", 5 "), 6.66 (s, 1H, H-5), 6.58 (s, 1H, H-8), 6.31 (s, 2H, H-2 ', 6 '), 5.91 (m, 2H, OCH
2O), 4.91 (s, 2H,
CH 2 C
6H
4OCH
3), 4.42 (m, 1H, H-11), 4.36 (d, J=2.8Hz, 1H, H-1), 3.95 (m, 1H, H-4); 3.80 (s, 3H, C
6H
5O
CH 3 ), 3.74 (s, 6H, 3 ', 5 '-OCH
3), 3.32 (m, 1H, H-4); 2.88 (m, 1H, H-11), 2.82 (m, 1H, H-2); 2.45 (m, 1H, H-3).
4), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 527.
5), reaction formula is:
Compound 27:
The physico-chemical property of this compound is as follows:
1), yellow solid, 219 ℃ of fusing points, specific rotatory power [α]
20 D=-102 ° (C=1.1mg/mL, chloroform);
2), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.31 (d, J=8.4Hz, 2H, H-3 ", 5 "), 7.64 (d, J=8.4Hz, 2H, H-2 ", 6 "), 6.67 (s, 1H, H-5), 6.51 (s, 1H, H-8), 6.36 (s, 2H, H-2 ', 6 '), 5.93 (d, J=9.2Hz, 2H, OCH
2O), 5.06 (s, 2H,
CH 2 C
6H
4NO
2), 4.60 (s, 1H, H-1), 4.43 (m, 1H, H-11), 3.90 (m, 1H, H-11), 3.73 (s, 6H, 3 ', 5 '-OCH
3), 3.05 (m, 1H, H-4); (2.67 m, 3H, H-2,3,4).
3), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 542.
4), reaction formula is:
Compound 28:
The physico-chemical property of this compound is as follows:
1), yellow solid, 218 ℃ of fusing points, specific rotatory power [α]
20 D=+20 ° (C=5.1mg/mL, chloroform);
2), the nuclear magnetic resonance map of this compound (
1HNMR, 400MHz) feature:
With the deuterochloroform is solvent, and TMS is interior mark, and wherein each peak ownership is: δ: 8.20 (d, J=8.4Hz, 2H, H-2 ", 6 "), 7.66 (d, J=8.8Hz, 2H, H-3 ", 5 "), 6.67 (s, 1H, H-5), 6.55 (s, 1H, H-8), 6.35 (s, 2H, H-2 ', 6 '), 5.92 (m, 2H, OCH
2O), 5.08 (s, 2H,
CH 2 C
6H
4NO
2), 4.43 (m, 1H, H-11), 4.35 (d, J=3.2Hz, 1H, H-1), 3.97 (m, 1H, H-4); 3.76 (s, 6H, 3 ', 5 '-OCH
3), 3.30 (m, 1H, H-4); 2.97 (m, 1H, H-11), 2.83 (m, 1H, H-2); 2.47 (m, 1H, H-3).
3), ESI-TRAP source mass spectrum (MS) the figure feature of this compound: its [M+Na]
+The peak is 542.
4), reaction formula is:
Embodiment 2:
Of the present invention giving birth to surveyed experiment:
1, for the examination insect: 3 ages are armyworm larvae in earlier stage, is provided by insectary, Xibei Univ. of Agricultural ﹠ Forest Science ﹠ Technology public nuisance-free agricultural chemicals research centre.
2, sample and reagent:
Sample is: Toosendanin, deoxidation podophyllotoxin, 4 '-the go compound 1-28 of first deoxidation podophyllotoxin and embodiment preparation.Solvent is an acetone, the Long Huagongshijichang of Chengdu section, analytical pure.
3, give birth to the survey method:
Adopt leaflet butterfly additive process: at diameter is shop, culture dish bottom one deck filter paper of 9 centimetres, and adds water and preserve moisture.The armyworm larvae in early stage in 3 ages that 10 sizes of every ware picking are consistent, healthy and strong.Take by weighing 5mg Toosendanin, deoxidation podophyllotoxin, 4 '-remove first deoxidation podophyllotoxin and compound 1-28 respectively, add 5ml acetone, be made into the soup that concentration is 1mg/ml.Leaf of Semen Maydis is cut into 1 * 1 centimetre little leaf butterfly, in soup to be measured, soaked 3 seconds, dry the back and feed the examination worm.With the acetone solution is the blank group.10 of every processing repeat 3 times.In under the room temperature (about 25 ℃), humidity 65%～80%, light application time is to raise under 12 hours/12 hours the condition.Feed with normal leaf butterfly until emergence after 48 hours.The food ingestion of periodic logging insect, survivor of a murder attempt's number, reveal any symptoms etc. calculate examination 24 hours, 48 hours food refusal rate of worm and final mortality ratio according to following formula.Measurement result sees Table 1.
Food refusal rate (%)=(the average food ingestion of the average food ingestion-treatment group of control group)/(the average food ingestion of control group) * 100
Final mortality ratio (%)=(the dead number of examination worm)/(the total number of examination worm) * 100
Correct mortality ratio (%)=(handling mortality ratio-contrast mortality ratio)/(1-contrasts mortality ratio) * 100
Table 1 the present invention 4 '-go first deoxidation podophyllotoxin derivative 1-28 to 3 age mythimna separata the food refusal toxic effect
Conclusion: the result shows that 16,48 hours the antifeedant activity of compound of the present invention's preparation is higher than Toosendanin, and the cytotoxicity of compound 2,10,13,14,16,17,24,25,27 all is higher than Toosendanin and parent compound.
Claims (6)
1.4 '-'-podophyllotoxin demethyl deoxidated aromatic ester, substituted benzene sulfonate and ether derivative is characterized in that, its chemical general formula is:
C-2 position in the chemical general formula is the α configuration, and C-4 ' bit substituent R is:
C-2 position in the chemical general formula is a beta comfiguration, and C-4 ' bit substituent R is:
2. the preparation method of the described 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester of claim 1, substituted benzene sulfonate and ether derivative is characterized in that, comprising:
The preparation of a, 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester analog derivative 1,3-16:
With 4 '-go first deoxidation podophyllotoxin, aromatic acid and 4-Dimethylamino pyridine to be dissolved in the dichloromethane solvent, at room temperature add dewatering agent N after the stirred for several minute, N '-sec.-propyl carbodiimide, then reaction is placed ice-water bath, TLC follows the tracks of detection, and reaction finishes after-filtration, remove di-isopropyl urea solid, use dichloromethane extraction after adding entry in the filtrate, use anhydrous sodium sulfate drying after merging organic phase, behind the concentrated evaporate to dryness with the preparation silica gel thin sheet separate required pure product;
B, 4 '-the go preparation of first deoxidation podophyllotoxin substituted benzenesulfonic acid ester derivative 17-24:
Toward 4 '-go to add triethylamine in the first deoxidation podophyllotoxin dichloromethane solution, under ice-water bath, slowly drip the substituted benzene SULPHURYL CHLORIDE to it, dropwise afterreaction and place room temperature, TLC follows the tracks of detection, reaction adds entry stirred for several minute when finishing, dichloromethane extraction washs with saturated brine after merging organic phase, anhydrous sodium sulfate drying, concentrate behind the evaporate to dryness with the preparation silica gel thin sheet separate required pure product;
C, 4 '-the go preparation of first deoxidation podophyllotoxin ether derivative 26-28:
With 4 '-go the acetone soln of first deoxidation podophyllotoxin, methanesulfonates and salt of wormwood to reflux, TLC follows the tracks of detection, reaction finishes back evaporate to dryness reaction solution, add entry, the water dichloromethane extraction, use anhydrous sodium sulfate drying after merging organic phase, behind the concentrated evaporate to dryness with the preparation silica gel thin sheet separate required pure product.
3. method as claimed in claim 2 is characterized in that, and is described 4 '-as to go the preparation method of first deoxidation podophyllotoxin to be:
The liquid bromine is slowly splashed in the naphthane solution that is mixed with iron powder, the bromize hydrogen gas that produces feeds in the dark cold-trap after passing through the wash bottle that fills naphthane solution, the hydrogen bromide feeding of overflowing from cold-trap contains 1 of deoxidation podophyllotoxin and ether, in the 2-dichloroethane solution, stirring reaction under the ice-water bath; TLC follows the tracks of detection, and reaction adds equal proportion when complete substantially water, acetone soln and barium carbonate stirred 30 minutes; The reaction solution ethyl acetate extraction, organic phase is washed with saturated brine, anhydrous sodium sulfate drying, concentrate evaporate to dryness after silica gel column chromatography separate required pure product.
4. method as claimed in claim 3 is characterized in that, the preparation method of described deoxidation podophyllotoxin may further comprise the steps:
Podophyllotoxin and 10% palladium carbon were reacted in autoclave 5 hours with hydrogen under 2 normal atmosphere, 95 ℃ condition in glacial acetic acid solution, reaction finishes the after-filtration reaction solution, remove palladium carbon, the filtrate decompression distillation, solvent evaporated after silica gel column chromatography separate crude product, get required pure product through recrystallizing methanol again.
5. method as claimed in claim 2 is characterized in that, used aromatic acid, substituted benzene SULPHURYL CHLORIDE and methanesulfonates are respectively:
A, aromatic acid are: toluylic acid, p-methylbenzoic acid, m-methyl benzoic acid, anisic acid, 0-chloro-benzoic acid, m-chlorobenzoic acid, Chlorodracylic acid, naphthylacetic acid, M-NITROBENZOIC ACID, p-nitrobenzoic acid, 3,5-dinitrobenzoic acid, styracin, nicotinic acid, 3-indolebutyric acid or Yi Yansuan;
B, substituted benzene SULPHURYL CHLORIDE are: m-nitrobenzene sulfonyl chloride, benzene sulfonyl chloride, to anisole SULPHURYL CHLORIDE, m-chloro p-nitrophenyl SULPHURYL CHLORIDE, parachloroben-zenesulfonyl chloride, p-methyl benzene sulfonic chloride, to ethylbenzene SULPHURYL CHLORIDE or p-bromobenzenesulfonyl chloride;
C, methanesulfonates are: methylsulfonic acid to methoxy benzyl ester or methylsulfonic acid to the nitrobenzyl ester.
6. the described 4 '-'-podophyllotoxin demethyl deoxidated aromatic ester of claim 1, substituted benzene sulfonate and the ether derivative application that is used to prepare plant insecticide.
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| CN102093382B (en) * | 2011-02-14 | 2012-10-24 | 西北农林科技大学 | 2alpha or 2beta-bromopodophyllotoxin derivatives, preparation thereof, and application thereof to botanical pesticides |
| CN102260273B (en) * | 2011-05-13 | 2015-04-22 | 兰州大学 | Deoxypodophyllo and 5-fluorouracil spliced compounds and preparation and application thereof |
| CN102349549A (en) * | 2011-09-07 | 2012-02-15 | 刘长禄 | Pesticide prepared from plant source and alphacypermethrin |
| CN102633808B (en) * | 2012-05-03 | 2014-02-26 | 浙江尖峰药业有限公司 | Manufacturing method for deoxypodophyllotoxin |
| CN103214495A (en) * | 2013-03-29 | 2013-07-24 | 西南交通大学 | Anti-cancer 4'-demethylation-4'-oxy-cyclobutyl formyl-deoxidation podophyllotoxin and preparation method thereof |
| CN103304574A (en) * | 2013-03-29 | 2013-09-18 | 西南交通大学 | Anticancer 4'-nor-anthricin and preparation method thereof |
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