CN1193979C - Jasmine keto ester derivatives and their use in plant cell - Google Patents

Jasmine keto ester derivatives and their use in plant cell Download PDF

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CN1193979C
CN1193979C CN 03129466 CN03129466A CN1193979C CN 1193979 C CN1193979 C CN 1193979C CN 03129466 CN03129466 CN 03129466 CN 03129466 A CN03129466 A CN 03129466A CN 1193979 C CN1193979 C CN 1193979C
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plant cell
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CN1470494A (en
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钱旭红
钟建江
赵振江
钱志刚
徐玉芳
田文红
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Dalian University of Technology
East China University of Science and Technology
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Dalian University of Technology
East China University of Science and Technology
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Abstract

The present invention discloses a structure of a novel jasmone acid ester compound and an application thereof in the growth promotion of the secondary metabolite of a plant cell. A yew (T. chinensis) cell of the China is selected by the present invention as an application system, and a jasmone acid methyl ester (MJA) structure is used as a precursor, and a series of plant cell inductive agents are designed and synthesized by leading in precursors containing fluorine, hydroxy groups and some plant growth regulators. An experimental result indicates that the performance of partial inductive agents is superior to the performance of MJA in the aspect of the biosynthesis promotion of taxane, and have conference value.

Description

Improved jasmonate derivatives and the application in vegetable cell thereof
Technical field
The present invention relates to novel jasmonic acid ester compound of a class and uses thereof.
Background technology
The abundant plant resources of nature is containing a considerable number of secondary metabolite, comprising the pharmaceuticals of many costlinesses.In order to develop these valuable resources, maybe might carry out the chemosynthesis except extracting from material of vegetable origin, the external large scale culturing technology of vegetable cell also is an effective approach.Utilize inductor to carry out the concern that secondary metabolite regulation and control have obtained more and more Chinese scholars, and become one of important method that increases substantially secondary metabolite content in the culture (Xie Qiuling, Guo Yong, Food science, 1998,19 (10), 7-9).
Taxol is the secondary metabolite that contains in the class Chinese yew genus plants, owing to its unique anticancer mechanism and curative effect, is considered to cancer patients's choice drug at present.According to estimates, the sales volume of taxol in 2000 reaches 1,600,000,000 US dollars (A.M.Thayer.Chem.Eng.News., 2000,78 (45), 20).Therefore, the various countries scientific research personnel has carried out extensive studies to the output that how to improve taxol.Because Chinese yew poor growth and distribution are narrow, directly extraction can't be satisfied market demand and unfavorable to environment.Though it is complete synthesis finishes, productive rate is too low can't realize mass production ((1) R.A.Holton, C.Somoza, et al., J.Am.Chem.Soc., 1994,116,1957, (2) K.C.Nicolaou, Z.Yang, et al., Nature, 1994,367,630).At present, most taxols and taxol precursor compound all are to utilize various yew plant cells to cultivate acquisition under the inductor effect.
The inductor that utilizes yew plant cells to cultivate taxol generally divides two kinds, promptly biological and abiotic inductor.The biotic induce agent has bacterium, true Jun and yeast; Abiotic inductor has various organic acids such as Whitfield's ointment, 2,4-D, arachidonic acid etc., rare earth metal salt such as cerous nitrate, Silver Nitrate etc.Up to the present, induce effect best be methyl jasmonate (MJA).((1)Y.Yukimune，H.Tabata，et?al.，Nat.Biotechnol.，14(1996)，110-118(2)R.E.B.Ketchum，D.M.Gibson，R.B.Croteau，M.L.Shuler，，Biotechnol.Bioeng.62，97-105，1999)。Methyl jasmonate is an isolated compound odorous from Largeflower Jasmine Flower (Jasminium Gradiflrum) volatile oil at first, also is the important component of jasminine peat-reek.It has very important physiological function, and it has the effect of plant-growth regulator, be the very popular class aromatic compounds of Recent study (guest Jinhua, BULLETIN OF BOTANY Vol., 1995,12 (4), 17-21).It still is the very important plant signal transduction molecule of a class, can excite the disease resistance response (the SAR-system obtains resistance) of plant.Making cell produce anaphylaxis in cell cultures, cause the pathways metabolism of cell and metabolic flux to change, is the inductor of excellent property.People also once made some changes to the natural structure of MJA, attempted to find the better MJA derivative of performance, but existing MJA derivative after modified induce all undesirable (the Otto Miersch of performance, Robert Kramell, et al., Phytochem., 50 (1999), 353-61).
The present invention chooses Chinese Ramulus et folium taxi cuspidatae (T.chinensis) cell as application system, based on the MJA structure, and, hydroxyl fluorine-containing and some plant-growth regulator precursors, design, synthetic a series of vegetable cell inductors by introducing.Experimental result shows: several compounds wherein are better than methyl jasmonate (MJA) in effect aspect the biosynthesizing that promotes Taxan, have suitable practical value.
Jasmonic acid ester compound involved in the present invention has following structural formula:
In the formula: R is OCH 2CF 3, OCH 2CF 2CF 3, OCH 2C 6F 5Or O (CH 2CH 2O) nR 1
R 1For
Figure C0312946600042
Or N=1,2 or 3
Preferred R is OCH 2CF 3, OCH 2CF 2CF 3, OCH 2C 6F 5Or O (CH 2CH 2O) nR 1,
R wherein 1Be 2-hydroxy benzoyl or phendioxin, 2,3-thiadiazoles-7-formyl radical, n=1,2, or 3.The synthetic route of above-claimed cpd:
With the methyl jasmonate is raw material, forms jasmonic acid through hydrolysis, with solid phosgene ((Cl 3CO) 2CO) reaction makes the jasmonic acid acyl chlorides, obtains the purpose product with corresponding pure esterification again.
Specific implementation method
The present invention is further illustrated below by embodiment, and the cited case does not limit protection scope of the present invention:
Embodiment one
Synthesizing of jasmonic acid trifluoro ethyl ester (compound 1):
Jasmonic acid (JA) 1.7mmol is dissolved in 20ml exsiccant CH under stirring 2Cl 2In, add 0.56mmol solid phosgene ((Cl 3CO) 2CO) and 3D DMF, add drying tube, argon shield refluxed 18 hours down slightly, be added drop-wise to after the cooling in the solution of forming by 2ml trifluoroethanol and 0.5ml triethylamine, and about 1 hour of dropping time, and then stirred 3 hours.Reaction mixture is poured in the separating funnel, uses the distilled water wash three times of twice at every turn, obtains light brown CH 2Cl 2Solution, anhydrous MgSO 4Dried overnight obtains the sticking shape liquid of brown after the filtering and concentrating.Column chromatography for separation twice obtains weak yellow liquid 0.11 gram, yield 22.6%.
1H?NMR(SF：500MHz，DMSO-d 6)，δ(ppm)，5.36-5.41(q，1H，J 1＝7.34Hz，J 2＝10.74Hz，J 3＝7.33Hz)，5.19-5.13(q，1H，J 1＝7.64Hz，J 2＝10.56Hz，J 3＝7.70Hz)，4.72-4.78(q，2H，J 1＝9.10Hz，J 2＝9.11Hz，J 3＝9.11Hz)，2.78-2.81(q，1H，J 1＝4.23Hz，J 2＝11.56Hz，J 3＝4.24Hz)，2.43-2.46(t，1H，J 1＝6.16Hz，J 2＝9.64Hz)，2.24-2.26(m，4H)，1.97-2.10(m，5H)，1.42-1.52(m，1H)，0.87-0.90(t，3H，J 1＝7.48Hz，J 2＝7.51)。HRMS，m/e(mass/calc.mass，％)：M +(292.1273/292.1286，75.07)；C 12H 12O 2F +(245.0770/245.0789，11.67)，M +-C 4H 9/C 10H 10O 3F 3 +(235.0566/235.0582，13.84)；C 9H 11O 3F 3 +(224.0670/224.0649，56.50)；C 12H 17O 2 +(193.1229/193.1229，13.27)；C 10H 15O +(151.1134/151.1123，76.57)；C 3H 8O 2F +(95.0554/95.0508，25.86)；C 5H 7O +(83.0513/83.0497，100.00)。
Embodiment two
Synthesizing of jasmonic acid five fluorine propyl ester (compound 2):
Jasmonic acid (JA) acyl chlorides (preparation method is with embodiment one) dichloromethane solution is added drop-wise in the solution of being made up of 1ml five fluorine propyl alcohol and 0.6ml triethylamine, about 1.5 hours of dropping time, and then stirring at room 12 hours.Reaction mixture is poured in the separating funnel, uses the distilled water wash three times of twice at every turn, obtains light brown CH 2Cl 2Solution, anhydrous MgSO 4Dried overnight obtains the sticking shape liquid of brown after the filtering and concentrating.Column chromatography for separation obtains weak yellow liquid 0.14 gram, yield 24%.
1H?NMR(SF：500MHz，DMSO-d 6)，δ(ppm)，5.36-5.41(q，1H，J 1＝7.31Hz，J 2＝10.65Hz，J 3＝7.31Hz)，5.17-5.22(q，1H，J 1＝7.51Hz，J 2＝10.77Hz，J 3＝7.60Hz)，4.80-4.86(t，2H，J 1＝13.90Hz，J 2＝13.88Hz)，2.78-2.82(q，1H，J 1＝4.21Hz，J 2＝11.64Hz，J 3＝4.21Hz)，2.43-2.46(t，1H，J 1＝6.21Hz，J 2＝9.65Hz)，2.17-2.27(m，4H)，1.96-2.09(m，5H)，1.42-1.49(m，1H)，0.87-0.90(t，3H，J 1＝7.43Hz，J 2＝7.51)。HRMS，m/e(mass/calc.mass，％)：M +(342.1218/342.1254，51.53)；M +-H 2O(324.1124/324.1149，4.37)；M +-C 2H 5(13.0852/313.0863，7.36)；M +-C 5H 8(274.0611/274.0628，32.26)；C 12H 17O 2 +(193.1212/193.1229，21.12)，C 10H 15O +(151.1109/151.1134，64.67)；C 7H 9O +(109.0698/109.0653，16.44)；C 5H 7O +(83.0497/83.0497，100.00)。
Embodiment three
Synthesizing of jasmonic acid five fluoro-methylbenzyl esters (compound 3)
Except that substituting the trifluoroethanol with five fluoro-methylbenzyl esters, other condition obtains colourless liquid 0.19 gram, productive rate 29% with embodiment one.
1H?NMR(SF：500MHz，DMSO-d 6)，δ(ppm)，5.32-5.37(q，1H，J 1＝7.30Hz，J 2＝10.85Hz，J 3＝7.27Hz)，5.21(s，2H)，5.14-5.19(q，1H，J 1＝7.62Hz，J 2＝10.76Hz，J 3＝7.53Hz)，2.65-2.69(q，1H，J 1＝4.52Hz，J 2＝11.04Hz，J 3＝4.59Hz)，2.34-2.39(q，1H，J 1＝9.19Hz，J 2＝6.44Hz，J 3＝9.25Hz)，2.14-2.21(m，4H)，1.90-2.06(m，5H)，1.41-1.45(t，1H，J 1＝9.15Hz，J 2＝10.20Hz)，0.84-0.87(t，3H，J 1＝7.40Hz，J 2＝7.50)。HRMS，m/e(mass/calc.mass，％)：M +(390.1250/390.1254，44.46)；M +-H 2O(372.1149/372.1149，4.93)；M +-C 5H 8(322.0607/322.0617，15.08)；C 12H 17O 3 +(209.1187/209.1178，12.26)，C 7H 2F 5 +(181.0041/181.0077，100.00)；C 10H 15O +(151.1112/151.1123，24.95)；C 7H 9O 3 +(141.0550/141.0552，45.91)；C 10H 11 +(131.0891/131.0861，10.34)；C 6H 7O +(95.0519/95.0497，13.91)；C 5H 7O +(83.0498/83.0497，15.74)。
Embodiment four
Synthesizing of jasmonic acid sulfo-methyl esters (compound 4):
Jasmonic acid (JA) acyl chlorides (preparation method is with embodiment one) dichloromethane solution is added drop-wise in the 3ml 15% sodium methyl mercaptide solution, about 0.5 hour of dropping time, and then stirring at room 5 hours.Reaction mixture is poured in the separating funnel, uses the distilled water wash three times of twice, anhydrous MgSO at every turn 4Dried overnight obtains brown slime body after the filtering and concentrating.Column chromatography for separation obtains colourless liquid 0.14 gram, productive rate 34.3%.
1H?NMR(SF：500MHz，DMSO-d 6)，δ(ppm)，5.36-5.41(q，1H，J 1＝7.31Hz，J 2＝10.78Hz，J 3＝7.32Hz)，5.16-5.21(q，1H，J 1＝7.50Hz，J 2＝10.77Hz，J 3＝7.50Hz)，2.89-2.93(q，1H，J 1＝4.47Hz，J 2＝10.45Hz，J 3＝4.51Hz)，2.60-2.65(t，1H，J 1＝9.28Hz，J 2＝5.73Hz，J 3＝9.28Hz)，2.16-2.25(m，7H)，1.92-2.09(m，5H)，1.42-1.51(m，1H)，0.88-0.91(t，3H，J 1＝7.48Hz，J 2＝7.59)。HRMS，m/e(mass/calc.mass，％)：M +(240.1153/240.1184，64.56)；M +-H 2O(222.1093/222.1078，12.28)；C 8H 12O 2S +(172.0550/172.0558，46.32)，C 11H 17O +(165.1409/165.1279，56.38)；C 10H 15O +(151.1100/151.1123，100.00)；C 11H 11O +(135.0813/135.0810，70.24)；C 7H 9O +(109.0726/109.0653，46.27)；C 6H 7O +(95.0586/95.0497，48.46)；C 5H 8 +(68.0600/68.0626，10.13)。
Embodiment five
Synthesizing of jasmonic acid (JA) ethylene glycol ester (compound 5):
Jasmonic acid 5mmol and 15ml ethylene glycol mix, and argon gas is saturated down, adds vitriol oil 0.4ml, and heating in water bath is to 50-60 ℃, and in 7 hours reaction times, during cooling was fallen back, ethyl acetate 30ml * 3 extracted, NaHCO 3Solution is washed, and washes anhydrous MgSO 3-4 time 4Dried overnight obtains colourless oil liquid 1.1 grams, yield 85.0% after the filtering and concentrating.
1H?NMR(SF：500MHz，DMSO-d 6)，δ(ppm)：5.35-5.40(q，1H，J 1＝7.31Hz，J 2＝10.67Hz，J 3＝7.29Hz)，5.19-5.24(q，1H，J 1＝7.57Hz，J 2＝10.59Hz，J 3＝7.63Hz)，4.4.02-4.04(t，2H，J 1＝5.04Hz，J 2＝5.09Hz)，3.54-3.56(t，2H，J 1＝5.02Hz，J 2＝5.10Hz)，2.63-2.67(q，1H，J 1＝4.41Hz，J 2＝11.04，J 3＝4.38Hz)，2.30-2.35(q，1H，J 1＝9.26Hz，J 2＝6.12Hz，J 3＝9.30Hz)，2.20-2.25(m，4H)，1.95-2.20(m，5H)，1.39-1.48(m，1H)，0.89-0.90(t，3H，J 1＝7.54Hz，J 2＝7.53Hz)。HRMS，m/e(mass/calc.mass，％)：M +(254.1517/254.1518，87.15)；M +-H 2O/C 14H 20O 3(236.1372/236.1412，15.63)，M +-OC 2H 4OH/C 12H 17O 2(193.1203/193.1229，4.59)；C 10H 15O +(151.1092/151.1123，100.00)；C 6H 13O 3 +(133.0934/133.0865，29.36)；C 8H 9O +(121.0654/121.0653，19.11)；C 7H 9O +(109.0667/109.0653，28.28)；C 6H 7O +(95.0491/95.0497，29.20)；C 5H 7O +(83.0481/83.0497，47.39)。
Embodiment six
Synthesizing of jasmonic acid dimerization ethylene glycol ester (compound 6):
Jasmonic acid 1.67mmol and 6ml two polyoxyethylene glycol mix, and argon gas is saturated to add 6 of the vitriol oils down, and heating in water bath is to 60-70 ℃, to going in the 20ml distilled water anhydrous Na 2CO 3Neutralization, ethyl acetate 15ml * 3 extractions, NaHCO 3Solution is washed, and washes anhydrous MgSO 3-4 time 4Dried overnight obtains colourless oil liquid 0.41 gram, yield 82.5% after the filtering and concentrating.
1H?NMR(SF：500MHz，DMSO-d 6)，δ(ppm)，5.35-5.39(q，1H，J 1＝7.32Hz，J 2＝10.78Hz，J 3＝7.23Hz)，5.18-5.23(q，1H，J 1＝7.49Hz，J 2＝10.75Hz，J 3＝7.52Hz)，4.13-4.14(t，2H，J 1＝4.61Hz，J 2＝4.82Hz)，3.58-3.60(t，2H，J 1＝4.80Hz，J 2＝5.58Hz)，3.46-3.48(t，2H，J 1＝4.80Hz，J 2＝4.58Hz)，3.40-3.42(t，2H，J 1＝4.88Hz，J 2＝5.01Hz)，2.64-2.68(q，1H，J 1＝4.36Hz，J 2＝10.98Hz，J 3＝4.40Hz)，2.31-2.36(q，1H，J 1＝9.23Hz，J 2＝6.11Hz，J 3＝9.25Hz)，2.15-2.25(m，4H)，1.92-2.08(m，5H)，1.42-1.46(m，1H)，0.88-0.91(t，3H，J 1＝7.54Hz，J 2＝7.52Hz)。HRMS，m/e(mass/calc.mass，％)：M +(298.1794/298.1790，31.18)；M +-H 2O/C 16H 24O 4(280.1737/280.1675，4.95)，M +-OC 2H 4OH(237.1520/237.1491，7.73)；C 12H 16O 2 +(192.1195/192.1150，21.41)；C 10H 15O +(151.1126/151.1123，100.00)；C 6H 12O 4 +(148.0575/148.0736，33.58)；C 10H 13 +(133.1073/133.1017，22.15)；C 7H 9O +(109.0710/109.0653，23.51)；C 6H 7O +(95.0532/95.0497，26.58)；C 5H 7O +(83.0502/83.0497，31.07)。
Embodiment seven
Synthesizing of 1-jasmonic acid-2-(2 hydroxybenzoic acid) second diester (compound 7):
Whitfield's ointment 5 grams add 20ml dry benzene and 10ml SOCl 2, oil bath reflux 5 hours.Cooling, underpressure distillation benzene and unreacted SOCl 2, obtain colourless liquid 4.6 grams.
Take by weighing top synthetic Whitfield's ointment acyl chlorides 1.4mmol, add dry toluene 5ml, this drips of solution is added to the frozen water refrigerative jasmonic acid ethylene glycol ester 1.2mmol, and in the solution of toluene 5ml and triethylamine 0.4ml, add half an hour.Remove ice bath, continue to stir 16 hours, TLC controls reaction.Reaction mixture is poured in the water, ethyl acetate 30ml * 2 extractions, washing twice, anhydrous MgSO 4Dried overnight obtains brown liquid after the filtering and concentrating, the preparation plate separates, and obtains pale yellow oily liquid body 0.11 gram, yield 33%.
1H NMR (SF:500MHz, DMSO-d 6), δ (ppm), 10.43 (s, 1H), 7.74-7.76 (d, 1H, J=7.94Hz), 7.51-7.54 (t, 1H, J 1=8.20Hz, J 2=7.28Hz), and 6.97-6.99 (d, 1H, J=8.32Hz), 6.92-6.94 (t, 1H, J 1=7.55Hz, J 2=7.49Hz), and 5.31-5.33 (q, 1H), 5.14-5.16 (q, 1H), and 4.51-4.53 (t, 2H), 4.398-4.40 (t, 2H), and 2.65-2.69 (q, 1H), 2.31-2.36 (q, 1H), and 2.10-2.22 (m, 4H), 1.90-2.04 (m, 5H), 1.39-1.44 (quintet, 1H), and 0.82-0.85 (t, 3H).HRMS，m/e(mass/calc.mass，％)：M +(374.1715/374.1729，12.52)；M +-C 5H 8(306.1079/306.1103，15.35)；C 14H 8O 4 +(240.0423/240.0423，12.64)；C 9H 9O 3 +(165.0555/165.0552，14.72)；C 10H 15O +(151.1115/151.1123，9.80)；C 7H 5O 2 +(121.0281/121.0290，100.00)。
Embodiment eight
Synthesizing of 1-jasmonic acid-2-(phendioxin, 2,3-thiadiazoles-7-formic acid) second diester (compound 8):
By 0.56mmol 7-carboxyl phendioxin, 2, the acyl chlorides of 3-thiadiazoles preparation is dissolved in the 1.5ml exsiccant toluene, at ambient temperature, be added drop-wise to jasmonic acid (JA) ethylene glycol ester 6.2mmol, in the solution that dry toluene 1.5ml and 0.15ml triethylamine are formed, about 30 minutes of dropping time.Continue reaction 20 hours then.Reaction mixture is poured in the frozen water into ethyl acetate 20ml * 2 extractions, washing twice, anhydrous MgSO 4Dried overnight obtains colourless oil liquid after the filtering and concentrating, 300-400 order silica gel column chromatography separates, and obtains a small amount of colourless liquid.
1H NMR (SF:500MHz, DMSO-d 6), δ (ppm) 9.04-9.06 (d, 1H, J=8.33Hz), 8.40-8.41 (d, 1H, J=7.29Hz), 7.93-7.96 (t, 1H, J 1=7.82Hz, J 2=7.80Hz), and 520-5.25 (q, 1H), 5.07-5.12 (q, 1H), and 4.64-4.65 (t, 2H), 4.45-4.46 (t, 2H), and 2.65-2.66 (q, 1H), 2.32-2.37 (q, 1H), and 2.11-2.18 (m, 4H), 1.80-2.03 (m, 4H), and 1.37-1.45 (sextet, 1H), 1.06-1.08 (t, 1H), and 0.75-0.79 (t, 3H).HRMS，m/e(mass/calc.mass，％)：M +(416.1423/416.1406，14.05)；M +-C 5H 8/C 16H 16N 2O 5S(348.0736/348.0780，100.00)，M +-C 10H 14O/C 11H 10N 2O 4S(266.0328/266.0361，90.32)；C 9H 9N 2O 3S +(225.0331/225.0334，41.11)；C 9H 7N 2O 2S +(207.0246/207.0228，19.76)；C 7H 5N 2O 2S +(181.0121/181.0072，29.70)；C 7H 3OS +(134.9928/134.9905，52.71)；C 6H 3S +(106.9988/106.9955，17.70)；C 6H 7O +(95.0524/95.0497，10.75)。
Embodiment nine
1-jasmonic acid-2 '-(2 hydroxybenzoic acid) dimerization ethylene glycol diester (compound 9) synthetic:
Jasmonic acid (JA) acyl chlorides (preparation method is with embodiment one) dichloromethane solution is added drop-wise to by 0.4 gram Whitfield's ointment tirethylene glycol monoesters (1.77mmol), in the solution that 10ml methylene dichloride and 0.5ml triethylamine are formed, added stirring at room reaction 10 hours in 30 minutes.Washing, anhydrous magnesium sulfate drying.Obtain brown slime body after the filtering and concentrating.Column chromatography for separation obtains a small amount of weak yellow liquid.
1H NMR (SF:500MHz, DMSO-d 6), δ (ppm), 10.47 (s, 1H), 7.78-7.79 (d, 1H, J=7.92Hz), 7.51-7.54 (t, 1H, J 1=8.40Hz, J 2=7.11Hz), and 6.92-6.98 (m, 2H), 5.31-5.33 (q, 1H), 5.32-5.40 (q, 1H, J 1=13.41Hz, J 2=14.71Hz, J 3=11.26Hz), 5.15-5.23 (q, 1H, J 1=13.01Hz, J 2=15.17Hz, J 3=10.76Hz), 4.41-4.43 (t, 2H, J 1=4.32Hz, J 2=4.67Hz), 4.15-4.17 (t, 2H, J 1=4.21Hz, J 2=5.11Hz), 3.76-3.78 (t, 2H, J 1=4.70Hz, J 2=4.42Hz), 3.66-3.68 (t, 2H, J 1=4.44Hz, J 2=4.95Hz), and 2.58-2.62 (q, 1H), 2.29-2.58 (m, 1H), 1.86-2.07 (m, 10H), 1.36-1.42 (quintet, 1H), 0.85-0.88 (t, 3H, J 1=7.37Hz, J 2=7.39Hz).HRMS，m/e(mass/calc.mass，％)：M +(418.1798/418.1992，13.83)；M +-C 5H 8(50.1375/350.1366，2.70)；C 16H 26O 5 +(298.1876/298.1780，9.10)；C 14H 20O 5 +(268.1276/268.1311，2.94)；C 11H 15O 5 +(227.0994/227.0919，3.76)；C 12H 16O 2 +(192.1241/192.1150，4.86)；C 9H 9O 3 +(165.0582/165.0552，11.56)；C 7H 5O 2 +(121.0310/121.0290，100.00)；C 6H 4O +(92.0296/92.0262，6.37)。
Jasmonic acid ester compound Application Example (cultivation of taxus chinensis cell, the production of Tc and measuring method referring to the clock Kien Giang, Dong Haodi, Chinese invention patent application number 00125305.0):
Embodiment ten
The taxus chinensis cell that employing obtains from plant children stem explant induction callus.The 250mL shake-flask culture adopts the MS substratum, and other adds the 0.5mg/L 6-benzyladenine, 0.2mg/L 2,4 dichlorophenoxyacetic acid, 0.2mg/L naphthylacetic acid, 100mg/L xitix and 30mg/L sucrose.
The 5g wet cell that vacuum filtration is obtained is inoculated into and contains the shaking in the bottle of the above-mentioned substratum of 50mL, secretly cultivates in rotary shaking speed is 110rpm, 25 ℃.First group in contrast; Second group added at the 7th day MJA to ultimate density be 100 μ M; The 3rd group was added compound 1 to ultimate density at the 7th day is 100 μ M; The 4th group was added compound 5 to ultimate density at the 7th day is 100 μ M; The 5th group was added compound 7 to ultimate density at the 7th day is 100 μ M; The 6th group was added compound 8 to ultimate density at the 7th day is 100 μ M, continues to be cultured to end in the 21st day, and harvested cell also is dried to constant weight at 40 ℃.Each organizes cell density and the Tc analytical results is as shown in the table.
The highest Tc turnout of the highest Tc content of maximum cell density
Condition
(gDW·L -1) [mg·(gDW) -1] (mg·L -1)
First group of (contrast) 15.3 ± 0.2 (day 12), 14.0 ± 0.1 (day 21) 149 ± 4 (day 21)
Second group of (MJA) 15.3 ± 0.1 (day 12), 33.7 ± 1.6 (day 18) 402 ± 22 (day 18)
The 3rd group of (compound 1) 15.1 ± 0.2 (day 12) 39.7 ± 1.1 (day 21) 440 ± 6 (day 18)
The 4th group of (compound 5) 14.6 ± 0.2 (day 12) 44.3 ± 1.1 (day 21) 472 ± 12 (day 15)
The 5th group of (compound 7) 14.8 ± 0.1 (day 12) 40.3 ± 0.6 (day 21) 434 ± 8 (day 12)
The 6th group of (compound 8) 13.9 ± 0.2 (day 12) 39.6 ± 0.8 (day 18) 427 ± 15 (day 18)
Embodiment 11
Culture condition is with example ten.First group in contrast; Second group at the 7th day interpolation compound 2 to 100 μ M; The 3rd group was added compound 6 to 100 μ M at the 7th day, continued to be cultured to end in the 21st day.Each organizes cell density and the Tc analytical results is as shown in the table.
The highest Tc turnout of the highest Tc content of maximum cell density
Condition
(gDW·L -1) [mg·(gDW) -1] (mg·L -1)
First group of (contrast) 16.3 ± 0.1 (day 12), 13.0 ± 0.0 (day 21) 182 ± 16 (day 15)
Second group of (compound 2) 16.3 ± 0.1 (day 12), 38.2 ± 1.7 (day21) 480 ± 25 (day 21)
The 3rd group of (compound 6) 13.1 ± 0.2 (day 21) 34.2 ± 0.1 (day 21) 464 ± 17 (day 15)
Embodiment 12
Culture condition is with example ten.First group in contrast; Second group at the 7th day interpolation compound 4 to 100 μ M; The 3rd group was added compound 9 to 100 μ M at the 7th day, continued to be cultured to end in the 21st day.Each organizes cell density and the Tc analytical results is as shown in the table.
The highest Tc turnout of the highest Tc content of maximum cell density
Condition
(gDW·L -1) [mg·(gDW) -1] (mg·L -1)
First group of (contrast) 15.6 ± 1.0 (day 12), 9.8 ± 0.1 (day 18) 139 ± 1 (day 18)
Second group of (compound 4) 14.6 ± 0.2 (day 15), 30.9 ± 2.5 (day 21) 380 ± 26 (day 18)
The 3rd group of (compound 9) 14.8 ± 1.0 (day 12) 31.4 ± 1.4 (day 21) 381 ± 27 (day 21)
Embodiment 13
Culture condition is with example ten.First group in contrast; The second-five group was added compound 1 to ultimate density at the 7th day respectively is 1,10,100,500 μ M, continues to be cultured to end in the 21st day.Each organizes cell density and the Tc analytical results is as shown in the table.
The highest Tc turnout of the highest Tc content of maximum cell density
Condition
(gDW·L -1) [mg·(gDW) -1] (mg·L -1)
First group of (contrast) 16.1 ± 0.5 (day 12), 11.8 ± 2.2 (day 21) 147 ± 24 (day 21)
Second group (1 μ M) 16.1 ± 0.3 (day 12) 13.1 ± 0.5 (day 21) 167 ± 5 (day 21)
The 3rd group (10 μ M) 16.2 ± 0.2 (day 12) 19.4 ± 3 (day 21) 261 ± 1 (day 21)
The 4th group (100 μ M) 15.6 ± 0.2 (day 12) 34.7 ± 0.3 (day 21) 404 ± 5 (day 21)
The 5th group (500 μ M) 13.2 ± 0.1 (day 12) 43.1 ± 0.3 (day 21) 406 ± 12 (day 21)
Embodiment 14
Culture condition is with example ten.First group at the 7th day interpolation sucrose 20g/L; Second group was added sucrose 20g/L at the 7th day, and added compound 1 to 100 μ M simultaneously, continued to be cultured to end in the 21st day.Each organizes cell density and the Tc analytical results is as shown in the table.
The highest Tc turnout of the highest Tc content of maximum cell density
Condition
(gDW·L -1) [mg·(gDW) -1] (mg·L -1)
First group of 24.6 ± 0.2 (day 18) 9.1 ± 0.9 (day 12) 171 ± 4 (day 21)
Second group of 21.9 ± 0.4 (day 15) 27.3 ± 1.1 (day 12) 564 ± 12 (day 18)

Claims (4)

1, a kind of jasmonic acid ester compound, it has following structural formula:
Figure C031294660002C1
In the formula: R is OCH 2CF 3, OCH 2CF 2CF 3, OCH 2C 6F 5Or O (CH 2CH 2O) nR 1
R 1For Or N=1,2 or 3.
2, compound as claimed in claim 1 is characterized in that, wherein R is OCH 2CF 3, OCH 2CF 2CF 3Or OCH 2C 6F 5
3, compound as claimed in claim 1 is characterized in that, wherein R is O (CH 2CH 2O) nR 1, R in the formula 1Be 2-hydroxy benzoyl or phendioxin, 2,3-thiadiazoles-7-formyl radical, n=1,2, or 3.
4, as claim 1～3 application of compound as described in each, described compound is used to promote the growth of vegetable cell secondary metabolite as the vegetable cell inductor.
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BRPI0619492A2 (en) * 2005-12-07 2011-10-04 Univ Ramot jasmonate chemical derivatives, pharmaceutical compositions and methods of use
US9284274B2 (en) 2005-12-07 2016-03-15 Ramot At Tel-Aviv University Ltd. Chemical derivatives of jasmonate, pharmaceutical compositions and methods of use thereof
WO2008151526A1 (en) * 2007-06-08 2008-12-18 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences A method of inducing taxane production
US9284252B2 (en) 2009-06-09 2016-03-15 Sepal Pharma Ltd. Use of jasmonate ester derivatives for treating benign hyperproliferative skin disorders

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