CN1083060A - The azlocillin that is used for Pest Control - Google Patents
The azlocillin that is used for Pest Control Download PDFInfo
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- CN1083060A CN1083060A CN 93109589 CN93109589A CN1083060A CN 1083060 A CN1083060 A CN 1083060A CN 93109589 CN93109589 CN 93109589 CN 93109589 A CN93109589 A CN 93109589A CN 1083060 A CN1083060 A CN 1083060A
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- ring
- thf
- tetrahydrofuran
- azlocillin
- glu
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Abstract
The invention discloses a kind of acetyl genin (Acetogenins) with tetrahydrofuran (THF) ring feature structure, its chemical structure pattern is: CH
3-(CXY)
m (CXY)
n-G, the optional following form of G:
X, Y can choose: H, H; H, OH; H, OAC;=O and H, O-glu (glu is a glucosyl group)
M=7～21; N=3～9; K=1 or 2
No more than 2 of glucosyl group number.
This product as cabbage caterpillar, small cabbage moth etc., has intensive food refusal effect and insecticidal activity to various pests.
Description
The present invention relates to a kind of azlocillin (Annonsil-ins) with tetrahydrofuran (THF) ring feature structure.
Annona lactone (Annonaceous acetogenins) is the peculiar compound of a class annonaceae plant.First compound Uvaricin[Jolad et al of this compounds, J.Org, Chem., 47:3151-3153(1982)] be found since, to 1986, successively found that Desacetyluvaricin, Rollinicin, Isorollinicin, Rollinon, Cherimoline and Dihydrocherimoline, these compounds have two tetrahydrofuran (THF)s and a saturated or unsaturated lactone ring five membered, and performance there is the activity of antagonism KB cell, 9PS, 3PS.Two United States Patent (USP)s (U.S.Patent No:4721727, Jan, 26,1988 that Mikolajczak etc. successively obtain 1988 and 1989; U.S.Patent No:4855319, Aug, 8,1989), its structural pattern is as follows:
The desirable form of A:
R
1R
2Can choose: H, H; H, OH; H, OAC and=0, R
1R
2Oxygen replaces sum≤6
M=9～15; N=10～18; R=1; W=1 or 2
When w=1, m+n+2r 25～29
During w=2, m+n+2r 21～25
Its shortcoming is dispersed relatively poor, and is lower to cabbage caterpillar (Piers rapea L.) and small cabbage moth (Plutella xylostella L.) killing action.
The object of the present invention is to provide a kind of azlocillin that cabbage caterpillar, small cabbage moth is had killing action.
Structural pattern of the present invention is:
The optional following form of G:
X, Y can choose: H, H; H, OH; H, OAC;=O and H, O-glu(glu are glucosyl group)
M=7～21; N=3～9; K=1 or 2
No more than 2 of glucosyl group number.
Be included in the structural pattern (I), its compound can be mentioned from sweetsop (Annona squamosaL.), corossol (Annona muricata L.) and Hainan brother receive kind seed of (Goniothalam-us howii Merr.et Chun).They contain a tetrahydrofuran (THF) ring or two adjacent tetrahydrofuran (THF) rings, the five-ring lactone of α, β who has a methyl-unsaturated or saturated or have the lactone ring five membered of acetonyl, and by 3～9 CH
2The carbochain of forming links together, and the position of tetrahydrofuran (THF) in whole carbochain partially toward lactone ring five membered one end, has hydroxyl, ketone group, acetoxyl group group usually usually on carbochain.Their chemical structural formula is:
Hainan brother receives fragrant fourth element (howiicin D) R=H, m=13, n=5(III)
Penta element (howiicin E) R=OH, m=11, n=7(IV)
Plain (howiicin F) R=OH, m=13, n=5(V)
Element in heptan (howwicin G) R=OH, m=13, n=5(VI)
Azlocillin first (Annonsilin A)
Compound of the present invention is dissolvable in water in organic solvents such as alcohols, acetone, chloroform, methylene dichloride, ether, ethyl acetate and the aqueous alcohol, also can be by surfactant-dispersed in water.They are based on one or more mechanism of action to the preventive and therapeutic effect of insect, comprise the food refusal effect, suppress some enzyme, suppress digestion, stomach toxicity and kill effect and other effects, especially food refusal, stomach toxicity to kill effect strong.The acetyl genin does not have the effect of tagging to cabbage caterpillar, small cabbage moth, therefore, helps the protection of pest natural enemy, helps the protection of human ecological environment, is particularly useful for the pest control of producing with people's daily life vegetables in close relations.
The compound pattern that the present invention proposes, except C, H, O, do not contain other chemical elements, the linear chemical structure of compound pattern helps these compounds in soil, under the sunlight, progressively degraded under field conditions (factors), and can not produce the objectionable impurities of contaminated soil, underground water, air and agricultural byproducts.The azlocillin compounds is also different with the toxicological effect of conventional chemical agricultural chemicals to the toxicity of insect, and the stomach toxicity effect of killing is based on the inhibition to the digestive ferment system of insect, therefore to human security.
The tetrahydrofuran (THF) ring is partial to lactone ring five membered one end in the structure formula I of The compounds of this invention pattern, therefore, helps rationally shortening the length of carbochain of the methyl end groups of non-active portion, the selection of synthesis material and chemosynthesis when helping chemosynthesis.
Embodiment one:
Separating step:
The extraction of vegetable material
The distinctive annonaceae plant Hainan brother of China of originating in Hainan Province receives and smashs (2.50kg) to pieces after the seed of perfume (or spice) (Goniothala-mus howti Merr.et Chun) dries naturally, put in the percolator, add sherwood oil (bp60～90 ℃) diacolation, 20 liters of transudates (F001); Continue and use the acetone diacolation, 20 liters of acetone transudates (F002).Sherwood oil transudate (F001) reclaims sherwood oil, and (3 liters) place cooling during to the about 3000ml of remaining part volume, adds 80% ethanol (V/V) extraction subsequently, uses 500ml at every turn, and totally 6 times, 3000ml.80% alcohol extraction part (F003) merges (F004) with acetone transudate (F002) enriched material, and remove ethanol under reduced pressure, do not add a small amount of sherwood oil after the ethanol aftertaste and further take off ester to having, resistates (F005) is used acetone solution, mix and stir with 250 gram silica gel then, fine ground standby after drying naturally.
The chromatography of F005
F005 part with cabbage caterpillar do food refusal, stomach toxicity kills activity test and is indicated as high activity partially, carries out silica gel column chromatography.1.50 kilograms in silica gel, dry column-packing, the silica-gel powder that is adsorbed with F005 places the silicagel column upper end, uses following elutriant wash-out in turn: sherwood oil, petroleum ether-ethyl acetate mixed solution (95: 5,90: 10,85: 15,80: 20,70: 30,50: 50), ethyl acetate is used ethanol elution at last.Partly obtained howiicins D, penta, and heptan (howiicins D, E, F and G) at 90: 10～50: 50 wash-outs of petroleum ether-ethyl acetate.
Howiicins D (Howiicin D), white crystals, mp95～96 ℃, [α]
D+ 25.07 ° of (CHCl
3), C
35H
64O
6(MW=580).Howiicins E (howi-icin E), white crystals, 102～104 ℃ of mp, [α]
D+ 15.79 ° of (CHCl
3), C
35H
64O
7(MW=596).Howiicins D, penta, and the chemical structure in heptan (Howiicins D, E, F and G) through infrared spectra (IR), mass spectrum (MS), proton nmr spectra (
1H-NMR) and carbon spectrum
13C-NMR) and the mass spectrum of their acetyl derivatives, proton nmr spectra are identified, after the research, determine as III, IV, V and VI respectively.
Embodiment two:
The processing of plant sample
The seed of sweetsop (Annona squamosa L.) dries naturally, smashs (2446 gram) to pieces, puts and uses 20 liters of cold diacolations (F001) of sherwood oil (60～90 ℃ of bp) in the percolator, continues with 20 liters of diacolations of acetone (F002).F001 adds the 600ml petroleum ether dissolution after contracting and steaming to no sherwood oil again, and with 90% methanol extraction 5 times, each 150ml, 750ml(F003 altogether).90% methanol extraction liquid (F003) is concentrated into no methyl alcohol and steams, and adds vinyl acetic monomer 100ml dissolving then, anhydrous sodium sulfate drying, and the filtered and recycled vinyl acetic monomer gets vinyl acetic monomer dissolving part 14.4 grams (F004) behind the evaporate to dryness.Acetone transudate (F002) concentrates removes acetone, adds 500ml sherwood oil (60～90 ℃ of bp) dissolving, and extracts repeatedly with 80% methanol solution, each 80ml, totally 10 times, 800ml.80% methanol solution partly removes methyl alcohol under reduced pressure, and resistates (F005) is used ethyl acetate extraction, and vinyl acetic monomer solution adds anhydrous sodium sulfate drying, filters, and reclaims vinyl acetic monomer to doing, and obtains vinyl acetic monomer part (F006) 34.5 grams.
The column chromatography of F004
F004 14.4 gram, with the small amount of acetone dissolving, silica gel 60 grams mix and stir, and dry also fine groundly naturally, carry out column chromatography.Silica gel 500 grams, dry column-packing, the silica gel of absorption F004 places the post upper end, and use following elutriant wash-out in turn: sherwood oil (60～90 ℃ of bp), vinyl acetic monomer-sherwood oil the mixed solvent, the vinyl acetic monomer that contain 5%, 10%, 15%, 20%, 30%, 50% vinyl acetic monomer, use the acetone wash-out at last, obtain respectively F011, F012, F013 ... F043, F044, F045 component.F038～F041 merging obtains 5.25 grams (F050).
The column chromatography of F050
F050 5.25 gram, with the small amount of acetone dissolving, 20 gram silica gel mix and stir, dry, pulverize and carry out column chromatography.Silica gel 210 gram, dry column-packing, the silica-gel powder that is adsorbed with F050 places the upper end of post, and uses following elutriant wash-out in succession successively: sherwood oil (60～90 ℃ of bp), contain the sherwood oil mixed solvent of 5%, 8%, 10% acetone, use acetone at last.Obtain respectively F051, F052, F053 ... F063, F064, F065 component.In F057～F058 amalgamation liquid (F070), obtain compd A 4.
The purifying of A4
F057～F058 merging obtains F070, adds a little ether dissolution behind the evaporate to dryness and places crystallization, obtains A4 white crystals 35mg, 107～109 ℃ of mp, [α]
D+ 18.65 ° of (CHCl
3), C
37H
66O
7(MW=622).Through infrared spectra (IR), mass spectrum (MS), proton nmr spectra (
1H-NMR), carbon-13 nmr spectra (
13C-NMR) and the mass spectrum of its acetyl derivatives (MS), proton nmr spectra (
1H-NMR) analysis and research and structure are identified, the chemical structure of A4 is determined as VII, and called after azlocillin first (Annonsilin A).
Claims (2)
1, a kind of azlocillin that is used for Pest Control, the structural pattern that it is characterized by it is:
Optional following form:
X, Y can choose: H, H; H, OH; H, OAC;=O and H, O-glu (glu is a glucosyl group)
M=7～21; N=3～9; K=1 or 2
No more than 2 of glucosyl group number.
2, the azlocillin that is used for Pest Control according to claim 1, it is characterized by compound and contain a tetrahydrofuran (THF) ring or two adjacent tetrahydrofuran (THF) rings, the five-ring lactone of α, β who has a methyl-unsaturated or saturated or have the lactone ring five membered of acetonyl, and by 3～9 CH
2The carbochain of forming links together, and the position of tetrahydrofuran (THF) ring in whole carbochain partially toward lactone ring five membered one end, has hydroxyl, ketone group, acetoxyl group group usually usually on carbochain; Their chemical structural formula is:
Hainan brother receives fragrant fourth element (howiicin D) R=H, m=13, n=5
Penta element (howiicin E) R=OH, m=11, n=7
Plain (howiicin F) R=OH, m=13, n=5
Element in heptan (howwicin G) R=OH, m=13, n=5
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109589 CN1083060A (en) | 1993-08-13 | 1993-08-13 | The azlocillin that is used for Pest Control |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93109589 CN1083060A (en) | 1993-08-13 | 1993-08-13 | The azlocillin that is used for Pest Control |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1083060A true CN1083060A (en) | 1994-03-02 |
Family
ID=4987677
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93109589 Pending CN1083060A (en) | 1993-08-13 | 1993-08-13 | The azlocillin that is used for Pest Control |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1083060A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109678C (en) * | 1997-04-09 | 2003-05-28 | 中国科学院上海有机化学研究所 | Annona lactone analogue and its use |
| US6991818B2 (en) | 2001-03-30 | 2006-01-31 | Council Of Scientific & Industrial Research | Compound iso-squamocin obtained from seeds of annona squamosa and composition containing the same |
-
1993
- 1993-08-13 CN CN 93109589 patent/CN1083060A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109678C (en) * | 1997-04-09 | 2003-05-28 | 中国科学院上海有机化学研究所 | Annona lactone analogue and its use |
| US6991818B2 (en) | 2001-03-30 | 2006-01-31 | Council Of Scientific & Industrial Research | Compound iso-squamocin obtained from seeds of annona squamosa and composition containing the same |
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