CN1213660C - Ellipton cyclo dextrin or clathrate of cyclodextrin derivative and preparing method - Google Patents
Ellipton cyclo dextrin or clathrate of cyclodextrin derivative and preparing method Download PDFInfo
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- CN1213660C CN1213660C CN 02149737 CN02149737A CN1213660C CN 1213660 C CN1213660 C CN 1213660C CN 02149737 CN02149737 CN 02149737 CN 02149737 A CN02149737 A CN 02149737A CN 1213660 C CN1213660 C CN 1213660C
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- cyclodextrin
- rotenone
- inclusion compound
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Abstract
The present invention relates to the field of agricultural chemical, particularly to cyclodextrin of botanical insecticide, inclusion compounds of ramifications of the cyclodextrin, and a preparation method of the cyclodextrin and the inclusion compounds of the ramifications of the cyclodextrin. The rotenone cyclodextrin or the inclusion compounds of the ramifications of the cyclodextrin are prepared from rotenone, the cyclodextrin or the ramifications of the cyclodextrin by reacting in a coprecipitation method and a solid reaction process. After the inclusion compounds are formed by the rotenone, the rotenone in a hollow chamber is protected by the stereospecific blockade and complexation of the cyclodextrin so as to reduce the rate of degradation reaction of the rotenone, and the insecticide becomes stable. Simultaneously multiple hydroxyl outside the cyclodextrin hollow chamber is helpful to increase the dissolvability in water of the rotenone in the cavity. The rotenone cyclodextrin or the inclusion compounds of the ramifications of the cyclodextrin obtained from the present invention has the obvious function of killing pine wood nematode which is severely harmful to pinewood of China.
Description
Technical field
The invention belongs to pesticide field, particularly inclusion compound of the cyclodextrin of vegetable insecticide and derivative thereof and preparation method thereof.
Background technology
Vegetable insecticide is the main active insecticidal components that extracts from pesticide plant; because of its from plant; generally has higher safety; Environmental compatibility preferably; lower to the non-target organism influence, its mode of action and action site are various, and insect is difficult for producing advantages such as resistance; be the substitute that height poisons the medicine of learning to farm, aspect plant protection, obtained to use widely.Rotenone is early stage isolated a kind of high activity, broad spectrum insecticide, has higher insecticidal activity.Domestic existing multiple be that the insecticide of Main Ingredients and Appearance occurs with the rotenone, as Chinese patent disclosed 00107141.0,94100790.1; Also have obtaining of some rotenone or its missible oil product that is mixed to register and be extensive use of.But because of in the molecular structure of rotenone, having the active α hydrogen atom and the ring strain of unsaturated bond, ehter bond, carbonyl, rotenone is under UV-irradiation, and degraded fast under conditions such as water, oxygen, high temperature, be unfavorable for the preservation of agricultural chemicals and the control of insect.Water insoluble because of rotenone in addition, generally need make the missible oil use by adding organic solvent, the environmental influence that a large amount of consumptions of organic solvent and solvent evaporates are brought has to be solved.
Summary of the invention
The objective of the invention is to propose a kind of cyclodextrin of rotenone or inclusion compound of cyclodextrin and preparation method thereof, to improve the stability of rotenone insecticide to the ultraviolet light and heat, prolong the lasting period of insecticide, simultaneously, improve the solvability of the rotenone insecticide that is insoluble in water to a certain extent.
The present invention is the inclusion compound of a kind of rotenone and cyclodextrin or cyclodextrine derivatives, the architectural feature of inclusion compound is, in the cavity of the derivative of cyclodextrin or cyclodextrin, form with the cyclodextrin is that host molecule, rotenone are the inclusion compound of guest molecule to the molecule of rotenone by inclusion.Wherein, the molecular proportion of rotenone and cyclodextrin or cyclodextrine derivatives is 1: 2, and promptly each rotenone molecule is by two cyclodextrin moleculars or cyclodextrine derivatives molecule institute inclusion.
As the derivative of the cyclodextrin of host molecule or cyclodextrin is beta-schardinger dextrin-, alpha-cyclodextrin, gamma-cyclodextrin, 2-hydroxy propyl-Beta cyclodextrin (Hp-β-CyD), 2,6-dimethyl-beta cyclodextrin (DM-β-CyD), glucosyl group cyclodextrin.Wherein beta cyclodextrin is cheap and easy to get, is the lapping of the host molecule of first-selection.
The present invention realizes by following technical method: with rotenone and cyclodextrin or cyclodextrine derivatives, and by coprecipitation, solid reaction process reaction, the cyclodextrin inclusion of generation rotenone.Said co-precipitation preparation method is, cyclodextrin placed reactor and is heated to more than 50 ℃ make saturated aqueous solution, and be 1: 1～8 rotenone solution of cyclodextrin amount of substance with the rotenone amount of substance of organic solvent dissolution, at N
2Or H
2Or CO
2The protection of gas slowly adds in the reactor down, continues the heated and stirred or the 1 ~ 24h that refluxes, and filters, and drying can get inclusion compound.(filtrate of filtering in suitability for industrialized production can replace water to recycle as the solution of next batch dissolving cyclodextrin).
Said method also can prepare chemical pure inclusion compound, and the preparation method is, is dried to constant weight with twice recrystallization of derivative raw material of cyclodextrin or cyclodextrin and at 110 ℃, is placed on reactor again, is dissolved in water and is heated to more than 50 ℃ and make saturated aqueous solution; Get the rotenone amount of substance and be half of derivative amount of substance of cyclodextrin or cyclodextrin, rotenone is dissolved in the organic solvent, at N
2Or H
2Or CO
2Solution with rotenone under the protection of gas slowly adds in the reactor; described organic solvent is any in acetone or ether, methyl alcohol, ethanol, propyl alcohol, pyridine, DMF, the acetonitrile; continue the heated and stirred or the 1～24h that refluxes, filtered while hot or cooling are left standstill the back and are filtered.Remove unreacted rotenone in the filter residue with a small amount of organic solvent eccysis, remove unreacted cyclodextrin in the filter residue only with a spot of washing again, drying promptly obtains the inclusion compound of the derivative of the cyclodextrin of rotenone or cyclodextrin.For preparing the inclusion compound of analytically pure rotenone, can be recrystallized to above-mentioned chemical pure inclusion compound, silicagel column separates or high performance liquid preparative chromatography separates and vacuum drying.
Described solid phase method is, the derivative of cyclodextrin or cyclodextrin is mixed with rotenone, adds that a spot of water is common to be ground 1 to 4 hour.Then, at N
2Or H
2Or CO
2Down heating 2～4 hours 80 ± 20 ℃ scope in of protection is placed in the vacuum drying chamber more than the dry 4h again, gets the cyclodextrin of rotenone and the inclusion compound of cyclodextrine derivatives; Wash to remove unreacted rotenone in the inclusion compound with ethanol or acetone and other organic solvent, remove unreacted cyclodextrin with Warm Wash again and get the cyclodextrin of chemical pure rotenone and the inclusion compound of cyclodextrine derivatives; Separate purification with recrystallization method, silicagel column method or preparative high-performance liquid chromatographic method and reversed-phased high performace liquid chromatographic, last vacuum drying gets the cyclodextrin of highly purified rotenone and the inclusion compound of cyclodextrine derivatives.
In the solid reaction process of rotenone and cyclodextrin and cyclodextrine derivatives, the mol ratio of rotenone and cyclodextrin is 1 in the reactant: 1-1: 8, and wherein best ratio is 1: 2, this is the molecular proportion of its inclusion compound just.On this ratio, rotenone obtains effective inclusion, and cyclodextrin is not waste also.
Embodiment
The beneficial effect that is brought after the invention process is: after the derivative of rotenone and cyclodextrin or cyclodextrin forms inclusion compound, because the branch ascus of cyclodextrin has been wrapped up rotenone on molecular level, degraded modes such as the illumination degrading that cyclodextrin has been avoided rotenone to the sterically hindered effect and the complexing of vegetable insecticide, hydrolysis, polymerization, oxidation, strengthened the stability of vegetable insecticide, the corresponding lasting period that prolongs insecticide.
The hydrophilic hydroxyl that much is in the molecule exocoel is arranged because of cyclodextrin molecular, for hydrophobic for the rotenone of utmost point low-solubility in the water, after its molecule enters the hydrophobicity inner chamber of cyclodextrin, rotenone is by means of cyclodextrin hydrophily shell, its water-soluble has significantly increased by 11 times, if used the fabulous 2-hydroxypropyl of dissolubility, 2, cyclodextrine derivatives such as 6-dimethyl-beta cyclodextrin, the raising of the solvability of rotenone in water is more remarkable, and this has also relatively improved the pesticide supplying effect of rotenone.
Experimental result by the rotenone inclusion compound for preparing of the described mode of invention has also proved the stability of increase insecticide in theory and the deduction of solvability.The ultraviolet light light durability experiment of rotenone and cyclodextrin inclusion compound thereof shows, shine rotenone and the inclusion compound thereof of 40 μ M simultaneously with the uviol lamp of 2 parallel 30W, the ultraviolet lamp tube center is 40cm apart from the liquid level of solution distance, measure the absorbance of each material at corresponding ultraviolet absorption peak place respectively with high performance liquid chromatography and calculate the content of rotenone 2 remaining under its different irradiation times with ultraviolet specrophotometer, the results are shown in Table 1.
The residual concentration (unit μ M) of the solution of the inclusion compound of table 1 rotenone and beta-schardinger dextrin-thereof under the UV-irradiation of different time.
| Insecticide and inclusion compound thereof | Measure wavelength nm | Residual concentration (μ M) | ||||
| 0 hour | 6 hours | 12 hours | 18 hours | 24 hours | ||
| The beta-CD inclusion rotenone Hp-β-CYD inclusion compound of rotenone rotenone | 297 297 297 | 40 40 40 | 24.2 36.4 34.7 | 15.7 32.9 31.3 | 9.7 29.0 27.5 | 7.3 26.8 25.1 |
The heat endurance of inclusion compound also is significantly increased, the Benexate Hydrochloride of the rotenone of sealing (adding small amount of acetone for increasing its solvability), rotenone, the aqueous solution of rotenone 2-hydroxypropyl inclusion compound 40 μ M are respectively 54 ± 2 ℃ of heating 14 days, except that the aqueous solution of rotenone from 40 μ M reduce to 31.9 μ M, the degraded of the Benexate Hydrochloride of rotenone, the rotenone 2-hydroxypropyl inclusion compound aqueous solution is all not obvious.
The present invention has also improved the solvability of vegetable insecticide rotenone effectively, rotenone is after forming host and guest's molecular clathrate with beta-schardinger dextrin-, Celsius 25 when spending, the polyhydric hydrophilic interaction of beta-schardinger dextrin-exocoel makes the water solubility of rotenone improve 52 times, with 2-hydroxypropyl inclusion rotenone the content of rotenone in the aqueous solution is reached more than 8%.Under the effect of surfactant or under the heating for dissolving state, the inclusion compound of these cyclodextrin can be soluble in water, directly is mixed with the applications of pesticide.Certainly, be that the mixed pesticide of main component also is feasible with the cyclodextrin inclusion compound of rotenone.
Compare with rotenone, after rotenone forms cyclodextrin inclusion compound, its biologically active there is certain influence, with the example that act as to pine wood nematode, separate from the lesion pine tree of gathering for examination pine wood nematode (Bursaphelenchus xylophilus) from camphorwood head town, Dongguan City, Guangdong Province, after the dish stey of cultivating with corn (Pestalotiasp.) is gone up cultivation (25 ℃) 10d, with improvement shellfish graceful funnel method separated and collected nematode, with aseptic water washing several all over after to be made into 10000 nematode liquid of every ml (mixing worm age) standby.Line determination of activity extremely to pine wood nematode.Method and fungi culture with reference to Kawazu etc.Adopting diameter is the culture dish of 6cm, with PDA culture medium inoculated culture plate pestalotia bacteria, cultivates 5d at 25 ℃ of constant incubators, and mycelia is covered with plate.In the middle of covering with the culture dish of mycelia, place the long 1cm of a fritter, the little square absorbent cotton piece of thick about 0.5cm.Draw the rotenone of the respective concentration that 0.5ml has been made into and the cyclodextrin inclusion compound solution or the suspension of rotenone with micro syringe, inject cotton piece, draw 0.1ml nematode liquid again and add cotton piece central authorities, 4 repetitions are established in every processing, compare with 5 water.Cultivate nematode 1,2,3,4d at 25 ℃ of constant incubators.Medium in the plate is all poured out, with the graceful funnel method of improvement shellfish separated and collected nematode and counting.Result such as table 2
The solution of the inclusion compound of table 2 rotenone and beta-schardinger dextrin-thereof is killed and the inhibitory action of growth and breeding pine wood nematode.
| Rotenone insecticide and inclusion compound thereof | Concentration μ M | Remaining pine wood nematode number (head) | ||||
| Before the examination | 24 hours | 48 hours | 72 hours | 96 hours | ||
| The beta-CD inclusion rotenone Hp-β of the beta-CD inclusion rotenone Hp-β of rotenone rotenone-CYD inclusion compound rotenone rotenone-CYD inclusion compound CK | 2.5 2.5 2.5 25 25 25 | 100 100 100 100 100 100 100 | 75 82 84 69 47 42 104 | 41 55 57 31 22 26 109 | 30 39 31 25 16 13 113 | 13 17 18 9 4 3 121 |
Rotenone with molar concentration is compared with its inclusion compound activity, the rotenone effect is slightly high when 2.5 μ M, the inclusion compound activity is higher when 25 μ M, and this has increased solvability after may forming inclusion compound with rotenone, and the transport properties that has improved in the drug line polypide is relevant.
In order to understand the present invention better, now be exemplified below, the present invention can realize by including but not limited to following example:
The prepared by co-precipitation method of the inclusion compound of the beta-schardinger dextrin-of example 1 rotenone:
Get beta-schardinger dextrin-(the Shanghai uncle is difficult to understand) recrystallization and be heated to constant weight for twice, 110 ℃, accurately take by weighing 0.01mol and place three-neck flask, add 50ml water heated and stirred to beta-schardinger dextrin-and all dissolve, continue to be warming up to 70 ℃, in three-neck flask, feed N
2Not oxidized with the protective reaction thing; 0.005mol rotenone 5ml acetone solution, add dropping funel, under stirring condition, splash in the flask that beta-schardinger dextrin-is housed; continue to stir 8 hours; solution is concentrated into 20ml under vacuum condition, after cooling to room temperature, places 4 ℃ of refrigerations and spend the night; filter out precipitation; and use earlier the 5ml alcohol flushing, the 10ml warm water washing is used in the back, places 90 ℃ vacuum drying oven to dry by the fire 4h again.Can obtain rotenone-cyclodextrin inclusion compound, the ratio rotenone of bimolecular amount of substance in its inclusion compound: beta-schardinger dextrin-is 1: 2, and product is a pale yellow powder.Required rotenone can extract in the leaf by the root of trifoliate jewelvine plant or Africa mountain soya bean in this preparation, the inclusion compound of the cyclodextrin or derivatives thereof of rotenone is a kind of pulvis that certain solubility is arranged in water, the OP-10 stirring and dissolving that the inclusion compound of rotenone beta-schardinger dextrin-s of 2 grams is dissolved in 10mol, the water strong agitation that adds 100ml more promptly becomes microemulsion, can be expelled in the pine tree body of suffering from pine nematode, injection orifice is 0.3 meter on distance ground, the pine wood nematode that can kill in 10 days.In addition, this microemulsion can also available water be converted and become to be made into 1: 1000-1: 4000 the aqueous solution is used to prevent and treat paddy rice and vegetable-crop pest-insect.
The solid reaction process of the inclusion compound of the HP-beta cyclodextrin of example 2 rotenone prepares pure inclusion compound.
Get the 2-hydroxypropyl (aldrich) of 0.01mol, the water that adds 10ml is stirred to evenly, accurately takes by weighing rotenone 0.005mol, grinds 2h jointly with the 2-hydroxypropyl, at N
2Protection down is heated to the mixture water-bath 100 ℃ of 4h. and is placed on to bleed earlier in the vacuum drying oven again and is heated to 110 ℃ of 4h again; Cooling, add in the ethanol flush away product of 5ml the not rotenone of inclusion, 60 ℃ of washings with 10ml remove unreacted rotenone again, inclusion compound water with rotenone dissolves at last, for obtaining more highly purified inclusion compound, inclusion compound can be dissolved in water, heating, with recrystallization method recrystallization twice, can obtain purity at 95% above inclusion compound.Use high performance liquid preparative chromatography, water with 80% methyl alcohol and 20% is eluent wash-out inclusion compound, collect eluent and crystal clathrate, last vacuum drying can get ratio that purity surpasses bimolecular amount of substance in 98% the inclusion compound and be the inclusion compound of 2-hydroxypropyl of 1: 2 rotenone.
Claims (5)
1, the inclusion compound of a kind of rotenone cyclodextrin or cyclodextrine derivatives, it is characterized in that, the molecule of rotenone by inclusion in the cavity of the derivative of cyclodextrin or cyclodextrin, formation is host molecule with the derivative of cyclodextrin or cyclodextrin, rotenone is the inclusion compound of guest molecule, wherein, the molecular proportion of rotenone and cyclodextrin or cyclodextrine derivatives is 1: 2, be that each rotenone molecule is by two cyclodextrin moleculars or cyclodextrine derivatives molecule institute inclusion, the derivative of described cyclodextrin or cyclodextrin is a beta-schardinger dextrin-, alpha-cyclodextrin, gamma-cyclodextrin, 2-hydroxy propyl-Beta cyclodextrin, 2,6-dimethyl-beta cyclodextrin, any in the glucosyl group cyclodextrin.
2, the preparation method of the inclusion compound of a kind of rotenone cyclodextrin or cyclodextrine derivatives, it is characterized in that, the derivative of cyclodextrin or cyclodextrin placed reactor and be heated to more than 50 ℃ make saturated aqueous solution, with the rotenone amount of substance of organic solvent dissolution be cyclodextrin or cyclodextrin the derivative amount of substance 1: the rotenone solution of 1-8, at N
2Or H
2Or CO
2The protection of gas slowly adds in the reactor down; continue heated and stirred or refluxed 1～24 hour; filter; drying can get inclusion compound; the molecular proportion of the inclusion compound of wherein said rotenone and cyclodextrin or cyclodextrine derivatives is 1: 2; be that each rotenone molecule is by two cyclodextrin moleculars or cyclodextrine derivatives molecule institute inclusion; the derivative of described cyclodextrin or cyclodextrin is beta-schardinger dextrin-, alpha-cyclodextrin, gamma-cyclodextrin, 2-hydroxy propyl-Beta cyclodextrin; 2; 6-dimethyl-beta cyclodextrin, any in the glucosyl group cyclodextrin.
3, the preparation method of the inclusion compound of a kind of rotenone cyclodextrin or cyclodextrine derivatives, it is characterized in that, be dried to constant weight with twice recrystallization of derivative raw material of cyclodextrin or cyclodextrin and at 110 ℃, be placed on reactor again, be dissolved in water and be heated to more than 50 ℃ and make saturated aqueous solution; Get the rotenone amount of substance and be half of derivative amount of substance of cyclodextrin or cyclodextrin, rotenone is dissolved in the organic solvent, at N
2Or H
2Or CO
2Solution with rotenone under the protection of gas slowly adds in the reactor; described organic solvent is an acetone; ether; methyl alcohol; ethanol; propyl alcohol; pyridine; N; dinethylformamide; in the acetonitrile any; continue heated and stirred or refluxed 1～24 hour; filtered while hot or cooling are left standstill the back and are filtered; with unreacted rotenone in a small amount of organic solvent eccysis filter residue; only remove unreacted cyclodextrin or cyclodextrine derivatives in the filter residue with a spot of washing again; the inclusion compound of the derivative of dry cyclodextrin that promptly obtains rotenone or cyclodextrin; for preparing the inclusion compound of analytically pure rotenone; can be recrystallized to above-mentioned chemical pure inclusion compound; silicagel column separates or high performance liquid preparative chromatography separates and vacuum drying; the molecular proportion of the inclusion compound of wherein said rotenone and cyclodextrin or cyclodextrine derivatives is 1: 2; be that each rotenone molecule is by two cyclodextrin moleculars or cyclodextrine derivatives molecule institute inclusion; the derivative of described cyclodextrin or cyclodextrin is a beta-schardinger dextrin-; alpha-cyclodextrin; gamma-cyclodextrin; 2-hydroxy propyl-Beta cyclodextrin; 2; 6-dimethyl-beta cyclodextrin, any in the glucosyl group cyclodextrin.
4, the inclusion compound preparation method of a kind of cyclodextrin of rotenone or cyclodextrine derivatives is characterized in that described solid phase preparation method is, the derivative of cyclodextrin or cyclodextrin is mixed with rotenone, adds that a spot of water is common to be ground 1 to 4 hour, then, and at N
2Or H
2Or CO
2Down heating 2～4 hours 80 ± 20 ℃ scope in of protection is placed in the vacuum drying chamber dryly more than 4 hours again, gets the cyclodextrin of rotenone or the inclusion compound of cyclodextrine derivatives; To remove unreacted rotenone in the inclusion compound, remove unreacted cyclodextrin with Warm Wash again or cyclodextrine derivatives gets the cyclodextrin of chemical pure rotenone or the inclusion compound of cyclodextrine derivatives with ethanol or washing with acetone; Use recrystallization method, silicagel column method or preparative high-performance liquid chromatographic method and reversed-phased high performace liquid chromatographic are separated purification, last vacuum drying gets the cyclodextrin of highly purified rotenone or the inclusion compound of cyclodextrine derivatives, the molecular proportion of the inclusion compound of wherein said rotenone and cyclodextrin or cyclodextrine derivatives is 1: 2, be that each rotenone molecule is by two cyclodextrin moleculars or cyclodextrine derivatives molecule institute inclusion, the derivative of described cyclodextrin or cyclodextrin is a beta-schardinger dextrin-, alpha-cyclodextrin, gamma-cyclodextrin, 2-hydroxy propyl-Beta cyclodextrin, 2,6-dimethyl-beta cyclodextrin, any in the glucosyl group cyclodextrin.
5, the cyclodextrin of rotenone according to claim 4 or cyclodextrin derivant clathrate method for making is characterized in that, rotenone is 1 with the ratio of the amount of substance of cyclodextrin in the reactant: 1-8.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101743959B (en) * | 2008-12-18 | 2012-10-10 | 张保银 | Inclusion complex with insecticidal activity |
| EP3183965A1 (en) * | 2015-12-23 | 2017-06-28 | Omya International AG | Composition for aquatic pest control |
| CN106614649B (en) * | 2016-12-02 | 2019-02-15 | 华东理工大学 | A kind of preparation of the cyclodextrin inclusion compound and its wettable powder of cycloxaprid |
| CN108085352A (en) * | 2018-01-24 | 2018-05-29 | 江南大学 | A kind of method of two enzymes method control cyclodextrin inclusion compound sustained release |
| WO2020084572A1 (en) * | 2018-10-24 | 2020-04-30 | Adama Makhteshim Ltd. | Use of cyclodextrins as agrochemical delivery system |
| CN115399332B (en) * | 2022-08-31 | 2024-01-26 | 河北科技大学 | Oxalin clathrate, preparation method thereof and composition containing same |
| CN115381964B (en) * | 2022-08-31 | 2024-05-14 | 河北科技大学 | Improved preparation method of oxawire phenol-cyclodextrin inclusion compound |
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