CN109400648A - Bilobalide J derivative and its preparation method and application - Google Patents
Bilobalide J derivative and its preparation method and application Download PDFInfo
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- CN109400648A CN109400648A CN201811404842.8A CN201811404842A CN109400648A CN 109400648 A CN109400648 A CN 109400648A CN 201811404842 A CN201811404842 A CN 201811404842A CN 109400648 A CN109400648 A CN 109400648A
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- bilobalide
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- MOLPUWBMSBJXER-YDGSQGCISA-N bilobalide Chemical compound O([C@H]1OC2=O)C(=O)[C@H](O)[C@@]11[C@@](C(C)(C)C)(O)C[C@H]3[C@@]21CC(=O)O3 MOLPUWBMSBJXER-YDGSQGCISA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 7
- 125000001118 alkylidene group Chemical group 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 229910052740 iodine Inorganic materials 0.000 claims description 7
- 241000661348 Leptocorisa acuta Species 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 238000010511 deprotection reaction Methods 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 241000209094 Oryza Species 0.000 description 12
- 235000007164 Oryza sativa Nutrition 0.000 description 12
- 235000009566 rice Nutrition 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 241000258937 Hemiptera Species 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229930184727 ginkgolide Natural products 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000004083 survival effect Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940126214 compound 3 Drugs 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 244000018633 Prunus armeniaca Species 0.000 description 2
- 235000009827 Prunus armeniaca Nutrition 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- -1 flavone compound Chemical class 0.000 description 2
- SQOJOAFXDQDRGF-MMQTXUMRSA-N ginkgolide-b Chemical compound O[C@H]([C@]12[C@H](C(C)(C)C)C[C@H]3OC4=O)C(=O)O[C@H]2O[C@]24[C@@]13[C@@H](O)[C@@H]1OC(=O)[C@@H](C)[C@]21O SQOJOAFXDQDRGF-MMQTXUMRSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 235000008100 Ginkgo biloba Nutrition 0.000 description 1
- 244000194101 Ginkgo biloba Species 0.000 description 1
- GXEAHRDOFNEYNX-UHFFFAOYSA-M P(=O)(OC)(OC)[O-].[Cl+] Chemical compound P(=O)(OC)(OC)[O-].[Cl+] GXEAHRDOFNEYNX-UHFFFAOYSA-M 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 description 1
- 208000007536 Thrombosis Diseases 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000008485 antagonism Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- 210000004556 brain Anatomy 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 208000015114 central nervous system disease Diseases 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- FVTHQGOGQRTOMY-UHFFFAOYSA-N dibenzyl chloromethyl phosphate Chemical compound C=1C=CC=CC=1COP(=O)(OCCl)OCC1=CC=CC=C1 FVTHQGOGQRTOMY-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000857 drug effect Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229930003944 flavone Natural products 0.000 description 1
- 235000011949 flavones Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 210000002216 heart Anatomy 0.000 description 1
- 230000000302 ischemic effect Effects 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 208000010110 spontaneous platelet aggregation Diseases 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
- C07F9/65615—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings containing a spiro condensed ring system of the formula where at least one of the atoms X or Y is a hetero atom, e.g. S
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
- A01N57/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds
- A01N57/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-oxygen bonds or phosphorus-to-sulfur bonds containing heterocyclic radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/22—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains four or more hetero rings
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Plant Pathology (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The embodiment provides a kind of bilobalide J derivatives and its preparation method and application, are related to compound field, invent to improve compound activity.The structural formula of the bilobalide J is such as shown in (I), wherein X is singly-bound, alkylidene or alkylene oxide group；Y is P or S, and m, n are respectively the integer of 1-2.The present invention can be used in crops.
Description
Technical field
The present invention relates to compound fields more particularly to a kind of bilobalide J derivative and its preparation method and application.
Background technique
Ginkgo biloba p.e includes flavone compound and Ginkgolid.Wherein Ginkgolid includes silver
Apricot lactone A (GA), ginkolide B (GB), ginkalide C (GC), bilobalide J (GJ), ginkgolides M (GM) and Bilobalide
(BB)。
Ginkgolides related preparations are widely used in clinic, the ischemics diseases such as the treatment heart, brain, blood vessel and central nervous system
Disease, therapeutic effect are significant.Have it is relevant the experimental results showed that, ginkgolides has the function of significant antagonism PAF, can be effective
The formation for preventing platelet aggregation and thrombus.
There are many insufficient in practical applications for existing ginkgolide compound, it is necessary to its structure is modified,
To find a kind of better compound.
Summary of the invention
The main purpose of the embodiment of the present invention is, provides a kind of bilobalide J derivative and preparation method thereof and uses
On the way.
The embodiment of the invention provides one kind bilobalide J derivative as shown in formula (I),
Wherein, X is singly-bound, alkylidene or alkylene oxide group；
Y is P or S, and m, n are respectively the integer of 1-2, such as m=1,2, n=1,2.
Optionally, Y P, m=1, n=2.
Optionally, Y S, m=2, n=1.
Optionally, X is-CH2-O-。
Optionally, X is-CH2-。
Optionally, X is-CH2-CH2-O-
Optionally, X is singly-bound.It is further alternative, Y P, m=1, n=2；Or Y is S, m=2, n=1.
The embodiment of the invention also provides a kind of if above-mentioned general formula provided in an embodiment of the present invention is the bilobalide J of (I)
The preparation method of derivative, the preparation method include:
Bilobalide J reacts with the compound that general formula is (II), obtains the bilobalide J derivative that general formula is (I),
Wherein Z is derived from Cl, Br, I,
The structural formula of bilobalide J is as follows:
The embodiment of the invention also provides a kind of if above-mentioned general formula provided in an embodiment of the present invention is that (I) bilobalide J spreads out
Another preparation method of biology,
Y is P, m 1, n 2, and the described method includes:
Bilobalide J reacts with the compound that general formula is (III), obtains the intermediate that general formula is (IV), wherein Z takes
It is singly-bound, alkylidene or alkylene oxide group from Cl, Br, I, X, R is selected from C1-5Alkyl or benzyl,
The intermediate that general formula is (IV) is subjected to deprotection reaction, obtains the bilobalide J derivative that general formula is (I).
Optionally, the R is selected from methyl or ethyl.
Optionally, the R is selected from benzyl.
The embodiment of the invention also provides a kind of with above-mentioned bilobalide J derivative provided in an embodiment of the present invention for preventing
Control the purposes of green rice bug.
The embodiment of the invention provides a kind of bilobalide J derivatives and its preparation method and application, and the derivative is in silver
Replaced on the hydroxyl of No. 10 positions of apricot lactone J, substituent group free end is phosphate group or sulfonic acid group, improves derivative
Water solubility, to improve the bioactivity and drug effect of derivative；In addition, derivative does not have a hydroxyl group No. 1 position, this point
Sub- design method makes during the preparation process, it is not easy to introduce No. 1 position and carry out the substituted by-product of hydroxyl, can be improved derivative
Yield.
Specific embodiment
The technical scheme in the embodiments of the invention will be clearly and completely described below, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
The bilobalide J derivative with logical formula (I) provided by the invention includes a variety of particular compounds, is illustrated below
It is bright.
The above is only exemplary illustrations, not delimit the scope of the invention, and those skilled in the art can be according to logical formula (I)
Obtain the derivative of more bilobalide Js.Such as the derivative of alkyl substitution or halogen substitution is carried out on carbon oxygen.Replace alkane
Base is, for example, methyl, ethyl, propyl, tert-butyl etc..Halogen is, for example, Cl, Br, I etc..
Bilobalide J can react the derivative for generating corresponding bilobalide J with the reaction of corresponding compound.Reaction is former
It manages as follows.Wherein, Z is derived from Cl, Br, I, and X is singly-bound, alkylidene or alkylene oxide group；Y is P or S, and m, n are respectively the integer of 1-2.
In addition, bilobalide J can also produce the derivative of corresponding bilobalide J by following reaction principle.
Firstly, the hydroxyl of the compound reacted with bilobalide J protect at ether, generate intermediate (IV), wherein
Z is derived from Cl, Br, I, and X is singly-bound, alkylidene or alkylene oxide group；Y is P, m, n 1, n 2；R is selected from C1-5Alkyl or benzyl,
Such as methyl, ethyl, benzyl etc..
Then, intermediate (IV) is deprotected, obtains final bilobalide J derivative.
The bilobalide J derivative that embodiment provides in order to better illustrate the present invention, below in above compound
In some be described in detail as specific embodiments.
The synthesis of 1 compound 1 of embodiment
Synthetic intermediate
300mg bilobalide J is taken to be dissolved in 10mL acetonitrile, solution is placed at -5 DEG C, and 0.15mL triethylamine is slowly added dropwise.
After being sufficiently mixed, 303mg chlorine dimethyl phosphate is slowly dropped in mixed solution, was reacted under room temperature (25 DEG C, similarly hereinafter)
Night, thin-layer chromatography and LC-MS monitoring reaction, obtain intermediate.
Deprotection reaction
In N2Under protection, intermediate is dissolved in 30mLCH2Cl2In, it stirs evenly at room temperature, by C3H9ClSi is added drop-wise to mixing
It is stirred 36 hours in solution, obtains compound 1.
The synthesis of 2 compound 2 of embodiment
300mg bilobalide J is dissolved in 30mL acetonitrile, is stirred at room temperature, is slowly added to 1140mg tri- under N2 protection
Ethamine.7mL acetonitrile solution dissolved with 1140mg chlorosulfonic acid is added in mixed solution, after being reacted 9 hours at 90 DEG C, is added
4mL acetonitrile solution dissolved with 570mg chlorosulfonic acid, the reaction was continued 30 hours, with thin-layer chromatography and LC-MS monitoring reaction.Reaction
After, it is cooled to room temperature, by 50mL CH2Cl2It is added to reaction system, extracted three times with water and merges water phase, is evaporated under reduced pressure
Obtain crude product.With reverse phase silica gel column purification crude product, compound 2 is obtained.
The synthesis of 3 compound 3 of embodiment
Synthetic intermediate
60% NaH of 300mg bilobalide J and 58.5mg are placed in 8mL anhydrous tetrahydro furan, are heated to 80 DEG C,
N2It is stirred evenly under protection, being slowly added to the anhydrous tetrahydrofuran solution of chloromethyl dibenzyl phosphate, (280mg is dissolved in 5mL
In), it is added dropwise to complete, continues stirring 10 hours at 80 DEG C.After being cooled to room temperature, 150mL water is added, is acidified to the hydrochloric acid of 2M
PH is about 1, is extracted with ethyl acetate four times, and organic phase is merged, dry with anhydrous sodium sulfate, is obtained in 585mg after vacuum distillation
Mesosome ginkolide B methyl acid phosphate dibenzyl base ester.
Deprotection reaction
Above-mentioned intermediate ginkolide B methyl acid phosphate dibenzyl base ester is dissolved in 25mL methanol, 25mLPd/C is added,
H2Under 10h is stirred at room temperature.It is filtered to remove Pd/C, filtrate is concentrated and 30mL water is added, is washed four times with ethyl acetate, water phase is concentrated
And it is dry, obtain compound 3.
Performance test
In order to better illustrate the beneficial effect of embodiment, performance test has been carried out to embodiment 1-3.
The compound 1 of Example 1 is dissolved in the water, and forms the aqueous solution of 80ppm.Ten green rice bugs are put into vessel
And fresh paddy rice greenery.Take 5mL spray solution in vessel.Daily replacement rice greenery, and record the survival of green rice bug.
The compound 2 of Example 2 is dissolved in the water, and forms the aqueous solution of 80ppm.Ten green rice bugs are put into vessel
And fresh paddy rice greenery.Take 5mL spray solution in vessel.Daily replacement rice greenery, and record the survival rate of green rice bug.
The compound 3 of Example 3 is dissolved in the water, and forms the aqueous solution of 80ppm.Ten green rice bugs are put into vessel
And fresh paddy rice greenery.Take 5mL spray solution in vessel.Daily replacement rice greenery, and record the survival rate of green rice bug.
Comparative example
Ten green rice bugs and fresh paddy rice greenery are put into vessel.5mL clear water solution is taken to be sprayed in vessel.Daily more
Rice greenery are changed, and record the survival rate of green rice bug.
The above description is merely a specific embodiment, but scope of protection of the present invention is not limited thereto, any
Those familiar with the art in the technical scope disclosed by the present invention, can easily think of the change or the replacement, and should all contain
Lid is within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. a kind of bilobalide J derivative as shown in formula (I),
Wherein, X is singly-bound, alkylidene or alkylene oxide group；
Y is P or S, and m, n are respectively the integer of 1-2.
2. bilobalide J derivative according to claim 1, which is characterized in that Y P, m=1, n=2.
3. bilobalide J derivative according to claim 1, which is characterized in that Y S, m=2, n=1.
4. bilobalide J derivative according to claim 1, which is characterized in that X is-CH2- O- or-CH2-CH2-O。
5. bilobalide J derivative according to claim 1, which is characterized in that X is singly-bound.
6. a kind of preparation method of the described in any item bilobalide J derivatives of claim 1-5, which is characterized in that the system
Preparation Method includes:
Bilobalide J reacts with the compound that general formula is (II), obtains the bilobalide J derivative that general formula is (I), wherein
Z is derived from Cl, Br, I,
7. a kind of preparation method of the described in any item bilobalide J derivatives of claim 1-5, which is characterized in that
Y is P, m 1, n 2, and the described method includes:
Bilobalide J reacts with the compound that general formula is (III), obtains the intermediate that general formula is (IV), wherein Z is derived from
Cl, Br, I, X are singly-bound, alkylidene or alkylene oxide group, and R is selected from C1-5Alkyl or benzyl,
The intermediate that general formula is (IV) is subjected to deprotection reaction, obtains the bilobalide J derivative that general formula is (I).
8. preparation method according to claim 7, which is characterized in that
The R is selected from methyl or ethyl.
9. preparation method according to claim 7, which is characterized in that
The R is selected from benzyl.
10. the purposes that the described in any item bilobalide J derivatives of claim 1-5 are used to prevent and treat green rice bug.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811404842.8A CN109400648A (en) | 2018-11-23 | 2018-11-23 | Bilobalide J derivative and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811404842.8A CN109400648A (en) | 2018-11-23 | 2018-11-23 | Bilobalide J derivative and its preparation method and application |
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| Publication Number | Publication Date |
|---|---|
| CN109400648A true CN109400648A (en) | 2019-03-01 |
Family
ID=65474774
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811404842.8A Pending CN109400648A (en) | 2018-11-23 | 2018-11-23 | Bilobalide J derivative and its preparation method and application |
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| Country | Link |
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Citations (3)
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| WO2007002410A2 (en) * | 2005-06-22 | 2007-01-04 | The Trustees Of Columbia University In The City Of New York | Core-modified terpene trilactones from ginkgo biloba extract and biological evaluation thereof |
| CN104098584A (en) * | 2013-04-03 | 2014-10-15 | 广东东阳光药业有限公司 | Ginkgolide B derivative and application thereof in medicines |
| CN106793778A (en) * | 2014-10-16 | 2017-05-31 | 巴斯夫欧洲公司 | Prevent and treat the method and pesticide combination of Pentatomiddae animal pest |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007002410A2 (en) * | 2005-06-22 | 2007-01-04 | The Trustees Of Columbia University In The City Of New York | Core-modified terpene trilactones from ginkgo biloba extract and biological evaluation thereof |
| CN104098584A (en) * | 2013-04-03 | 2014-10-15 | 广东东阳光药业有限公司 | Ginkgolide B derivative and application thereof in medicines |
| CN106793778A (en) * | 2014-10-16 | 2017-05-31 | 巴斯夫欧洲公司 | Prevent and treat the method and pesticide combination of Pentatomiddae animal pest |
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Application publication date: 20190301 |