CN103351289B - New Kosteletzkya virginica sesquiterpene compound, and preparation method and use thereof - Google Patents
New Kosteletzkya virginica sesquiterpene compound, and preparation method and use thereof Download PDFInfo
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- CN103351289B CN103351289B CN201310211385.1A CN201310211385A CN103351289B CN 103351289 B CN103351289 B CN 103351289B CN 201310211385 A CN201310211385 A CN 201310211385A CN 103351289 B CN103351289 B CN 103351289B
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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 field of natural product chemistry.It is characterized in that with the rhizome of halophytes kostelezkya virginica (Kosteletzkya virginica (L.) Presl.) for raw material, by natural product chemistry method extraction and isolation, the new needle juniper alkane type sesquiterpene compound of the one obtained, 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 the production of cotton, consumption and weaving big country.Cotton area 7000-8000 ten thousand mu plants throughout the year in China, total produces about 6,000,000 tons, and account for that the world always produces 1/4th.Cotton verticillium wilt after the U.S. is by Late Cambrian, spread to other Chan Mian states in the world in 1914 very soon.Nineteen thirty-five imports 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 part province, and after the nineties in 20th century, this disease has spread to national each cotton region, become affect current Cotton Production Major Diseases it.Verticillium is the soil-borne fungus vascular bundle diseases infected by root, and cotton leaf chlorosis can be caused after infecting to turn yellow, and wilting comes off, and cause plant dead time serious, serious threat output of cotton and fibrous quality, cause serious financial loss.Cotton verticillium wilt is the fungal disease 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 in disease-resistant cotton wild species, kind and Gossypium kindred plant, needle juniper alkane type sesquiterpene compound has killing action to verticillium dahliae, can be used for cotton verticillium wilt control.(Puckhaber，L.S.，Stipanovic，R.D.，and Bell，A.A.Kenaf Phytoalexin：Toxicity of o-Hibiscanone and ItsHydroquinone 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, and 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, and chemical structural formula is:
Kostelezkya virginica element (virginicin).
The preparation method of above-claimed cpd, it is characterized in that with the rhizome of kostelezkya virginica (Kosteletzkya virginica (L.) Presl.) for raw material, through the alcohol with 5 ~ 6 times of raw material volume, 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 extraction into ethyl acetate by 1: 1 ~ 3 volumes; Acetic acid ethyl ester extract obtains through column chromatography for separation.Column chromatography carrier is selected from one or more in silica gel, gel, reverse phase silica gel; Organic solvent comprises methyl alcohol, ethanol, sherwood oil, ethyl acetate; Extracting temperature is lower than 100 DEG C.
The present invention also measures the activity of the anti-verticillium dahliae of above-claimed cpd, its ED
50for 1.2ug/ml.
4, accompanying drawing illustrates:
The structural formula of Fig. 1, virginicin
The HR-ESI-MS spectrum of Fig. 2, virginicin
Fig. 3, virginicin's
1h-NMR composes
Fig. 4, virginicin's
13c-NMR composes
The hsqc spectrum of Fig. 5, virginicin
The HMBC spectrum of Fig. 6, virginicin
The ROESY spectrum of Fig. 7, virginicin
5, embodiment:
Embodiment 1
Fresh Kosteletzkya virginica root tuber (water content is 75%) 13 kilograms is cut into 5 centimeters every section, add 95% ethanol of 6 times of crude drug volumes, refluxing extraction 2 times, each 2h, merges crude extract, 70 DEG C are evaporated to 0.5 times of medicinal material amount volume, extraction into ethyl acetate is added 5 times again, combined ethyl acetate extraction liquid, concentrating under reduced pressure by 1: 2 volume, drying, obtains acetic acid ethyl ester extract 0.065 kilogram.This acetic acid ethyl ester extract, use 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 elutriant that component is similar, after concentrated, obtain Fr.-A ~ Fr.-F totally 6 parts.The method such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization again, be separated from Fr.II-E part and obtain compound virginicin (930mg), yield is 0.009% at integrated use various spectroscopic technique (MS, NMR, UV, IR) identified.
The physico-chemical property of virginicin and spectral data:
Yellow needles (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, tentatively judge that this compound is the aromatic compounds of phenolic hydroxy group.EI-MS m/z289 [M-H]
-, 274 [M-H-Me]
-, 291 [M+H]
+, showing 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) and δ
h: the fignal center of 13.63 (1H, s) phenolic hydroxyl group, δ
hoccur in extremely low field, suspection may be define intramolecular hydrogen bond, makes it move to low field orientation; δ
h: 10.99 (1H, s) are the fignal centers 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 the fignal centers of-OMe; δ
h: 2.43 (3H, s) are the fignal centers of methyl on aromatic nucleus; δ
h: 1.82 (6H, s) are the fignal centers of 2 symmetrical aliphatics methyl;
13c-NMR (CDCl
3, 125MHz) compose and have 3 i.e. δ of-CH with DEPT in conjunction with known
c: 197.5,126.5,114.8; 4-CH
3i.e. δ
c: 59.7,31.6 × 2,16.4; 9 quaternary carbons and δ
c: 164.7,154.9,148.3,140.5,126.1,123.0,121.1,111.1,74.1; Not containing-CH
2; Known in conjunction with hsqc spectrum again: δ
h: 10.99 (1H, s) and δ
c: 197.5 have relevant peaks to prove the existence of-CHO; δ
h: 8.43 (1H, s), 7.10 (1H, s) and δ
c: 126.5,114.8 have relevant peaks to prove C-3, and 5 are connected with hydrogen; δ
h: 3.74 (3H, s) and δ
c: 59.7 have relevant peaks to prove the existence of-OMe; δ
h: 2.43 (3H, s), 1.82 (6H, s) and δ
c: 16.4,31.6 × 2 have relevant peaks to prove the existence of 1 fragrant methyl and 2 aliphatics methyl.
Compose in conjunction with H-H COSY and δ in 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 race methyl should be connected on C-4; C-6 is connected to methyl.δ in being composed by HMBC
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, known C-1,2,3, and 4 that connect respectively is-CHO ,-OH ,-H ,-containing 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, known C-5, and 6,7 that connect respectively is-H ,-Me ,-OH; δ
h: 3.74 (3H, s ,-OMe) and 140.5 have relevant peaks, and that known C-8 connects is-OMe; δ
h: 1.82 (6H, s) and δ
c: 154.9,114.8,74.1 have relevant peaks, then combine
1h-NMR,
13the data (see table.2-1) of C-NMR and molecular weight information, that known C-4 position connects is-COH (CH
3)
2this compound is 8-methoxyl group-2,7-dihydroxyl-4-(1 '-hydroxyl-1 '-methyl-ethyl)-6-methyl isophthalic acid-naphthaldehyde in sum, finds after SCIfinder retrieval, 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)
HPLC method measures the purity of virginicin, and chromatographic condition is: chromatographic column C
18(Agilent Eclipse XDB-C
18, 4.6 × 250mm, 5 μm), column temperature: 35 DEG C, moving phase: acetonitrile-water gradient (0 ~ 15min acetonitrile is changed to 80% by 30%), flow velocity: 1.0mL/min, determined wavelength: 360nm, sample size: 5 μ l; Theoretical plate number calculates should be not less than 1000 by virginicin peak.The retention time of virginicin is 8.32min, and the purity calculating product by area normalization method is 97.8%.
Embodiment 2:
5 kilograms, fresh for kostelezkya virginica branch (water content is 80%) is cut into 10 centimeters every section, add the methyl alcohol of 5 times of crude drug volumes, refluxing extraction 3 times, each 1.5h, merge crude extract, 50 DEG C are evaporated to 1 times of medicinal material amount volume, extraction into ethyl acetate is added 3 times again by 1: 1 volume, combined ethyl acetate extraction liquid, concentrating under reduced pressure, obtains kostelezkya virginica acetic acid ethyl ester extract 9 grams.The method such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization again, is separated and obtains compound virginicin (400mg) from acetic acid ethyl ester extract, and yield is 0.01%, the HPLC purity detecting product is 98.8%.
Embodiment 3
1 kilogram, dry for kostelezkya virginica branches and leaves are cut into 3 centimeters every section, add 80% methanol/water of 6 times of crude drug volumes, refluxing extraction 2 times, each 2h, merge crude extract, 50 DEG C are evaporated to 1.5 times of medicinal material amount volumes, extraction into ethyl acetate is added 5 times again by 1: 2 volume, combined ethyl acetate extraction liquid, concentrating under reduced pressure, obtains acetic acid ethyl ester extract.The method such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization again, is separated and obtains compound virginicin (80mg) from acetic acid ethyl ester extract, and yield is 0.008%, the HPLC purity detecting product is 98.4%.
Embodiment 4
1 kilogram, dry for kostelezkya virginica branches and leaves 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, then add extraction into ethyl acetate 3 times by 1: 2 volume, combined ethyl acetate extraction liquid, concentrating under reduced pressure obtains acetic acid ethyl ester extract.The method such as integrated use silica gel column chromatography, gel LH-20 column chromatography, recrystallization again, is separated and obtains compound virginicin (40mg) from acetic acid ethyl ester extract, and yield is 0.004%, the HPLC purity detecting product is 97.5%.
Embodiment 5
The anti-verticillium dahliae determination of activity of virginicin
Verticillium dahliae V.dahliae is that Institute of Plant Protection of academy of agricultural sciences of Jiangsu Province is separated and obtains from the cotton field of the morbidity of Dafeng City of cotton main producing region, Jiangsu Province.
Verticillium dahliae is grown on PDA substratum (potato 200g, agar 179, sucrose 20g, tap water 1000ml), cultivates 7 days for 25 DEG C.Then by 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 DEG C of shaking culture 6-7 days.By verticillium dahliae system culture through four layers of filtered through gauze, add up filtrate spore count under the microscope, 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 substratum, makes the concentration of compound virginicin in substratum reach 5 different concns within the scope of minimum inhibitory concentration and blank.2,4-diacetyl Phloroglucinol is positive reference substance.Then be down flat plate, after condensation, inoculate verticillium dahliae, repeat 4 times, 28 DEG C of constant temperature culture, measure a verticillium dahliae bacterial plaque diameter, until the bacterial plaque of blank covers with flat board every 24h.The inhibiting rate of computerized compound virginicin, carries out regression analysis with statistical software, draws the suppression 50 1.143851e-144ffective concentration (ED of compound virginicin
50).Measurement result is as following table:
Claims (4)
1. a needle juniper alkane type sesquiterpene compound, called after kostelezkya virginica element virginicin, it is characterized in that chemistry 8-methoxyl group-2,7-dihydroxyl-4-(1 '-hydroxyl-1 '-methyl-ethyl)-6-methyl isophthalic acid-naphthaldehyde by name, chemical structural formula is:
Kostelezkya virginica element virginicin.
2. the preparation method of compound according to claim 1, it is characterized in that with the rhizome of kostelezkya virginica Kosteletzkya virginica (L.) Presl. for raw material, through the alcohol with 5 ~ 6 times of raw material volume, 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 extraction into ethyl acetate by 1: 1 ~ 3 volumes; Acetic acid ethyl ester extract obtains through column chromatography for separation.
3. preparation method according to claim 2, is characterized in that one or more that column chromatography carrier is selected from silica gel, gel, reverse phase silica gel; Organic solvent comprises methyl alcohol, ethanol, sherwood oil, ethyl acetate; Extracting temperature is lower than 100 DEG C.
4. compound according to claim 1 is in the purposes of preparation control cotton verticillium wilt agricultural chemicals.
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