CN103351289A - New Kosteletzkya virginica (L.) Presl. sesquiterpene compound, and preparation method and use thereof - Google Patents
New Kosteletzkya virginica (L.) Presl. sesquiterpene compound, and preparation method and use thereof Download PDFInfo
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Abstract
The invention discloses a new Kosteletzkya virginica (L.) Presl. sesquiterpene compound, and a preparation method and a use thereof, and belongs to the chemical field of natural products. The above new cadinane type sesquiterpene compound is obtained by extracting and separating from a raw material the rhizome of a halophyte Kosteletzkya virginica (L.) Presl. through chemical processes of the natural products. The structural formula of the compound is shown in the specification, is named as virginicin, has a strong killing effect on Verticillium dahliae, and can be used for controlling cotton verticillium wilt.
Description
1, technical field
The invention discloses a kind of new sesquiterpenoid and its production and use, belong to the natural product chemistry field.It is characterized in that rhizome take halophytes kostelezkya virginica (Kosteletzkya virginica (L.) Presl.) is as raw material, extract separation by the natural product chemistry method, a kind of new needle juniper alkane type sesquiterpene compound that obtains, called after kostelezkya virginica element (virginicin), this compound has stronger killing action to verticillium dahliae, can be used for the control of cotton verticillium wilt.
2, background technology
Cotton is global Important Economic crop, and China is production, consumption and the weaving big country of cotton.Ten thousand mu of cotton area 7000-8000 plant throughout the year in China, and approximately 6,000,000 tons of gross outputs account for 1/4th of world's gross output.Cotton verticillium wilt in 1914 after the U.S. is found first, spreading to very soon in the world, other produce cotton state.Nineteen thirty-five is imported China into along with introducing a fine variety cotton verticillium wilt from the U.S., and the 50-60 age in 20th century works the mischief in the part province, after the nineties in 20th century, this disease spread to the whole nation each cotton region, become the impact current Cotton Production Major Diseases it.Verticillium is the soil-borne fungus vascular bundle diseases that infects by root, can cause the flavescence of cotton leaf chlorosis after infecting, and wilting comes off, and causes plant dead when serious, and serious threat output of cotton and fibrous quality cause serious financial loss.Cotton verticillium wilt is the fungal disease that is caused by verticillium dahliae.Deuteromycotina (Deutermy-cotina) light color Cordycepps (Mmonilaceae) Verticillium that verticillium dahliae (Verticillium dahliae Kleb) belongs to fungi belongs to (Verticillium).Recent study shows that the needle juniper alkane type sesquiterpene compound has killing action to verticillium dahliae in disease-resistant cotton wild species, kind and the Gossypium kindred plant, can be used for the cotton verticillium wilt control.(Puckhaber，L.S.，Stipanovic，R.D.，and?Bell，A.A.Kenaf?Phytoalexin：Toxicity?of?o-Hibiscanone?and?Its?Hydroquinone?to?the?Plant?Pathogens?Verticillium?dahliae?and?Fusarium?oxysporum?f.sp.vasinfectum.Journal?of?Agricultural?and?Food?Chemistry，1998，46(11)：4744-4747；Veshkurova，O.，Golubenko，Z.，Pshenichnov，E.，Arzanova，I.，Uzbekov，V.，Sultanova，E.，Salikhov，S.，Williams，H.J.，Reibenspies，J.H.，and?Puckhaber，L.S.Malvone?A，a?phytoalexin?found?in<i>Malva?sylvestris</i>(family?Malvaceae).Phytochemistry，2006，67(21)：2376-2379.)
3, summary of the invention
The invention discloses a kind of needle juniper alkane type sesquiterpene compound, called after kostelezkya virginica element (virginicin), molecular weight is: 290, molecular formula is: C
16H
18O
5,
Chemistry is by name: 8-methoxyl group-2,7-dihydroxyl-4-(1 '-hydroxyl-1 '-methyl-ethyl)-6-methyl isophthalic acid-naphthaldehyde, chemical structural formula is:
Kostelezkya virginica element (virginicin).
The preparation method of above-claimed cpd, it is characterized in that rhizome take kostelezkya virginica (Kosteletzkya virginica (L.) Presl.) is as raw material, through with the alcohol of 5～6 times of raw material volumes, water or its mixture refluxing extraction 2-3 time, each 1-2 hour, united extraction liquid, be evaporated to 0.5-1.5 times of material quantity volume, add ethyl acetate extraction by 1: 1～3 volumes; Acetic acid ethyl ester extract gets through column chromatography for separation.Column chromatography is selected from silica gel, gel, the reverse phase silica gel one or more with carrier; Organic solvent comprises methyl alcohol, ethanol, sherwood oil, ethyl acetate; Extract temperature and be lower than 100 ℃.
The present invention also measures the activity of the beautiful Verticillium of the above-claimed cpd Chinese People's Anti-Japanese Military and Political College, its ED
50Be 1.2ug/ml.
4, description of drawings:
The structural formula of Fig. 1, virginicin
The HR-ESI-MS spectrum of Fig. 2, virginicin
Fig. 3, virginicin's
1The H-NMR spectrum
Fig. 4, virginicin's
13The C-NMR spectrum
The hsqc spectrum of Fig. 5, virginicin
The HMBC spectrum of Fig. 6, virginicin
The ROESY spectrum of Fig. 7, virginicin
5, embodiment:
13 kilograms of fresh roots of kostelezkya virginica (water content is 75%) are cut into 5 centimeters every section, 95% ethanol that adds 6 times of crude drug volumes, refluxing extraction 2 times, each 2h merges crude extract, 70 ℃ are evaporated to 0.5 times of medicinal material amount volume, add ethyl acetate extraction 5 times, combined ethyl acetate extraction liquid, concentrating under reduced pressure by 1: 2 volume again, drying obtains 0.065 kilogram of acetic acid ethyl ester extract.This acetic acid ethyl ester extract, use the silica gel column chromatography segmentation, with sherwood oil, petroleum ether-ethyl acetate (30: 1), petroleum ether-ethyl acetate (10: 1), petroleum ether-ethyl acetate (4: 1), petroleum ether-ethyl acetate (1: 1) eluant solution, merge the similar elutriant of component, get Fr.-A～Fr.-F totally 6 parts after concentrating.Methods such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization again, partly separate to obtain compound virginicin (930mg) from Fr.II-E, yield is 0.009% at the various spectroscopic techniques of integrated use (MS, NMR, UV, IR) identified.
The physico-chemical property of virginicin and spectral data:
Yellow needle (chloroform), the TLC vitriol oil-Vanillin shows orange, FeCl
3Colour developing is positive; UV λ max (MeOH) 228,279,363nm; IR (KBr) v
Max3245 (fignal centers of OH), 1620 (CO fignal centers), 1295 (the aromatic nucleus fignal center of oxidation) cm
-1, judge that tentatively this compound is the aromatic compounds of phenolic hydroxy group.EI-MS m/z289[M-H]
-, 274[M-H-Me]
-, 291[M+H]
+, show that its molecular weight is 290, HR-TOF-MS m/z291.1235[C
16H
18O
5+ H]
+, calcd291.1232 infers that the molecular formula of kvg-24 is C
16H
18O
5, degree of unsaturation is 8.
1H-NMR (CDCl
3, 500MHz) δ
H: the fignal center of 13.63 (1H, s) phenolic hydroxyl group, δ
HOccur at extremely low, suspection may be to have formed intramolecular hydrogen bond, and it is moved to low field orientation; δ
H: 10.99 (1H, s) are-fignal center of CHO; δ
H: 8.43 (1H, s), 7.10 (1H, s) they are the fignal centers of fragrant hydrogen; δ
H: 3.74 (3H, s) are-fignal center of OMe; δ
H: 2.43 (3H, s) are the fignal centers of methyl on the aromatic nucleus; δ
H: 1.82 (6H, s) are the fignal centers of the aliphatics methyl of 2 symmetries;
13C-NMR (CDCl
3, be δ with the DEPT spectrum in conjunction with as can be known 3-CH being arranged 125MHz)
C: 197.5,126.5,114.8; 4-CH
3Be δ
C: 59.7,31.6 * 2,16.4; 9 quaternary carbons are δ
C: 164.7,154.9,148.3,140.5,126.1,123.0,121.1,111.1,74.1; Do not contain-CH
2Again in conjunction with hsqc spectrum as can be known: δ
H: 10.99 (1H, s) and δ
C: 197.5 have relevant peaks to prove-existence of CHO; δ
H: 8.43 (1H, s), 7.10 (1H, s) and δ
C: 126.5,114.8 have relevant peaks proof C-3, and 5 are connected with hydrogen; δ
H: 3.74 (3H, s) and δ
C: 59.7 have relevant peaks to prove-existence of OMe; δ
H: 2.43 (3H, s), 1.82 (6H, s) and δ
C: 16.4,31.6 * 2 have the existence of relevant peaks 1 fragrant methyl of proof and 2 aliphatics methyl.
In conjunction with δ in H-H COSY spectrum and the ROESY spectrum
H: 8.43 (1H, s) and 1.82 (6H, s), 2.43 (3H, s) have relevant peaks and δ
H: 1.82 (6H, s) and 7.10 (1H, s) have relevant peaks to infer: the group of fatty family methyl should be connected on the C-4; Connecting methyl on the C-6.By δ in the HMBC spectrum
H: 13.63 (1H, s ,-OH), 10.99 (1H, s ,-CHO) and δ
C: 164.7,114.8,111.1 have relevant peaks and δ
H: 7.10 (1H, s) and δ
C: 164.7,121.1,111.1,74.1 have relevant peaks, C-1 as can be known, 2,3,4 connect respectively be-CHO ,-OH ,-H ,-contain the group of fat methyl; δ
H: 2.40 (3H, s ,-Me) and δ
C: 148.3,126.5,123.0 have relevant peaks and δ
H: 8.43 (1H, s) and δ
C: 154.9,148.3,126.1,16.4 have relevant peaks, C-5 as can be known, 6,7 connect respectively be-H-Me ,-OH; δ
H: 3.74 (3H, s ,-OMe) with 140.5 relevant peaks is arranged, what C-8 connected as can be known is-OMe; δ
H: 1.82 (6H, s) and δ
C: 154.9,114.8,74.1 have relevant peaks, again combination
1H-NMR,
13The data of C-NMR (referring to table.2-1) and molecular weight information, what the C-4 position connected as can be known is-COH (CH
3)
2, this compound is 8-methoxyl group-2 in sum, 7-dihydroxyl-4-(1 '-hydroxyl-1 '-methyl-ethyl)-6-methyl isophthalic acid-naphthaldehyde, after the SCIfinder retrieval, find, be a new compound, called after kostelezkya virginica element (virginicin).
Table 1 new compound kostelezkya virginica element (virginicin)
13C-NMR and
1H-NMR spectral data (CDCl
3)
The HPLC method is measured the purity of virginicin, and chromatographic condition is: chromatographic column C
18(Agilent Eclipse XDB-C
18, 4.6 * 250mm, 5 μ m), column temperature: 35 ℃, moving phase: acetonitrile-water gradient elution (0～15min acetonitrile is changed to 80% by 30%), flow velocity: 1.0mL/min detects wavelength: 360nm, sample size: 5 μ l; Theoretical plate number is calculated by the virginicin peak should be not less than 1000.The retention time of virginicin is 8.32min, and the purity of calculating product by area normalization method is 97.8%.
Embodiment 2:
The fresh branch of kostelezkya virginica 5 kilograms (water content is 80%) is cut into 10 centimeters every section, the methyl alcohol that adds 5 times of crude drug volumes, refluxing extraction 3 times, each 1.5h merges crude extract, and 50 ℃ are evaporated to 1 times of medicinal material amount volume, add ethyl acetate extraction 3 times by 1: 1 volume again, the combined ethyl acetate extraction liquid, concentrating under reduced pressure obtains kostelezkya virginica acetic acid ethyl ester extract 9 grams.The methods such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization separate obtaining compound virginicin (400mg) from acetic acid ethyl ester extract again, and yield is 0.01%, and the purity that HPLC detects product is 98.8%.
1 kilogram in the dried branches and leaves of kostelezkya virginica are cut into 3 centimeters every section, 80% methanol/water that adds 6 times of crude drug volumes, refluxing extraction 2 times, each 2h merges crude extract, and 50 ℃ are evaporated to 1.5 times of medicinal material amount volumes, add ethyl acetate extraction 5 times by 1: 2 volume again, the combined ethyl acetate extraction liquid, concentrating under reduced pressure obtains acetic acid ethyl ester extract.The methods such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization separate obtaining compound virginicin (80mg) from acetic acid ethyl ester extract again, and yield is 0.008%, and the purity that HPLC detects product is 98.4%.
1 kilogram in the dried branches and leaves of kostelezkya virginica are cut into 3 centimeters every section, add 5 times of water, refluxing extraction 3 times, each 2h, merge crude extract, be evaporated to 1.5 times of medicinal material amount volumes, add ethyl acetate extraction 3 times by 1: 2 volume again, the combined ethyl acetate extraction liquid, concentrating under reduced pressure obtains acetic acid ethyl ester extract.The methods such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization separate obtaining compound virginicin (40mg) from acetic acid ethyl ester extract again, and yield is 0.004%, and the purity that HPLC detects product is 97.5%.
The beautiful Verticillium determination of activity of the virginicin Chinese People's Anti-Japanese Military and Political College
Verticillium dahliae V.dahliae is that Institute of Plant Protection, academy of agricultural sciences, Jiangsu Province separates from the cotton field of the morbidity of Dafeng City of cotton main producing region, Jiangsu Province and obtains.
Verticillium dahliae grows on the PDA substratum (potato 200g, agar 179, sucrose 20g, tap water 1000ml), cultivates 7 days for 25 ℃.Then with the verticillium dahliae bacterium colony, be inoculated in the 250ml Florence flask that sterilized 100ml liquid nutrient medium (potato 200g, sucrose 20g, distilled water 1000ml) is housed, 25 ℃ shaking culture 6-7 days.With verticillium dahliae be culture through four layers of filtered through gauze, at microscopically statistics filtrate spore count, repeat for 3 times, being made into concentration is 1 * 10
7The spore suspension of spore/ml, now with the current.
Compound virginicin dissolve with methanol adds in the substratum, makes the concentration of compound virginicin in the substratum reach minimum inhibitory concentration and 5 interior different concns of blank scope.The positive reference substance of 2,4-diacetyl Phloroglucinol.Then be down flat plate, inoculate verticillium dahliae after the condensation, repeat 4 times, 28 ℃ of constant temperature culture are measured a verticillium dahliae bacterial plaque diameter every 24h, until the bacterial plaque of blank covers with flat board.The inhibiting rate of computerized compound virginicin carries out regression analysis with statistical software, draws the inhibition 50 1.143851e-144ffective concentration (ED of compound virginicin
50).Measurement result such as following table:
Claims (4)
1. needle juniper alkane type sesquiterpene compound, called after kostelezkya virginica element (virginicin), it is characterized in that chemistry 8-methoxyl group-2 by name, 7-dihydroxyl-4-(1 '-hydroxyl-1 '-methyl-ethyl)-6-methyl isophthalic acid-naphthaldehyde, chemical structural formula is:
Kostelezkya virginica element (virginicin).
2. the preparation method of compound according to claim 1, it is characterized in that rhizome take kostelezkya virginica (Kosteletzkya virginica (L.) Presl.) is as raw material, through with the alcohol of 5～6 times of raw material volumes, water or its mixture refluxing extraction 2-3 time, each 1-2 hour, united extraction liquid, be evaporated to 0.5-1.5 times of material quantity volume, add ethyl acetate extraction by 1: 1～3 volumes; Acetic acid ethyl ester extract gets through column chromatography for separation.
3. preparation method according to claim 2 is characterized in that column chromatography is selected from silica gel, gel, the reverse phase silica gel one or more with carrier; Organic solvent comprises methyl alcohol, ethanol, sherwood oil, ethyl acetate; Extract temperature and be lower than 100 ℃.
4. compound claimed in claim 1 is in the purposes of the anti-control cotton verticillium wilt agricultural chemicals of preparation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104138367A (en) * | 2014-08-15 | 2014-11-12 | 江苏省中国科学院植物研究所 | Application of kosteletzkya malvidin in preparation of medicines for preventing and treating inflammation-related diseases |
| CN105924356A (en) * | 2016-05-21 | 2016-09-07 | 云南省烟草农业科学研究院 | Sesquiterpenoid compound and preparation method and application thereof |
| CN107459446A (en) * | 2016-06-05 | 2017-12-12 | 复旦大学 | Needle juniper alkane type sesquiterpene compound and preparation method thereof and the purposes in pharmacy |
Citations (1)
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| CN1489904A (en) * | 2003-08-27 | 2004-04-21 | 吴云锋 | Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1489904A (en) * | 2003-08-27 | 2004-04-21 | 吴云锋 | Polyhydroxy binaphthalene fatty acid preparation and preparing method thereof |
Non-Patent Citations (3)
| Title |
|---|
| JOSEPH A.VEECHR,ET AL.: "Peroxidative Conversion of Hemigossypol to Gossypol.A Revised Structure for Isohemi goss ypol", 《J.C.S.CHEM.COMM.》, 31 December 1976 (1976-12-31), pages 144 - 145 * |
| LORRAINE S. PUCKHABER，ET AL.: "Kenaf Phytoalexin: Toxicity of o-Hibiscanone and Its Hydroquinone to the Plant Pathogens Verticillium dahliae and Fusarium oxysporum f. sp. vasinfectum", 《J.AGRIC.FOOD CHEM.》, vol. 46, no. 11, 31 December 1998 (1998-12-31), pages 4744 - 4747 * |
| OLGA VESHKUROVA，ET AL.: "Malvone A, a phytoalexin found in Malva sylvestris (family Malvaceae)", 《PHYTOCHEMISTRY》, vol. 67, 31 December 2006 (2006-12-31), pages 2376 - 2379 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104138367A (en) * | 2014-08-15 | 2014-11-12 | 江苏省中国科学院植物研究所 | Application of kosteletzkya malvidin in preparation of medicines for preventing and treating inflammation-related diseases |
| CN105924356A (en) * | 2016-05-21 | 2016-09-07 | 云南省烟草农业科学研究院 | Sesquiterpenoid compound and preparation method and application thereof |
| CN107459446A (en) * | 2016-06-05 | 2017-12-12 | 复旦大学 | Needle juniper alkane type sesquiterpene compound and preparation method thereof and the purposes in pharmacy |
| CN107459446B (en) * | 2016-06-05 | 2021-02-26 | 复旦大学 | Cadinane type sesquiterpenoids, preparation method thereof and application thereof in pharmacy |
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