CN1425293A - Nimbin cyclo-dextrin or derivative clathrate of cyclo-dextrin and preparing method - Google Patents
Nimbin cyclo-dextrin or derivative clathrate of cyclo-dextrin and preparing method Download PDFInfo
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- CN1425293A CN1425293A CN 02149738 CN02149738A CN1425293A CN 1425293 A CN1425293 A CN 1425293A CN 02149738 CN02149738 CN 02149738 CN 02149738 A CN02149738 A CN 02149738A CN 1425293 A CN1425293 A CN 1425293A
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- cyclodextrin
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Abstract
The present invention relates to farm chemical and especially plant pesticide clathrate and its preparation process. Through coprecipitation or solid phase reaction process, nimbin and cyclodextrin or its derivative are produced into clathrate, in which nimbin inside the cavity of cyclodextrin is protected by cyclodextrin with sterically hindered and complexing effect and thus has decreased degradation rate and stable pesticide effect. At the same time, the hydroxyl radicals outside the cyclodextrin cavity is favorable to raising the dissolvability of nimbin in water. Compared with nimbin, the clathrate of the present invention has longer effect lasting period.
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.Nimbin (azadirachtin) is to separate citrin class (1imonoid) compound of purifying out from seal chinaberry (Azadirachtaindica) seed, belongs to the tetracyclic triterpenes material.Because many tests confirm that it has the effect of strong antifeedant activity to desert locust (Schistocercagregaria), is named as " nimbin " subsequently; And later research confirms that it all has the effect of high bioactivity to multiple important crop pest, thereby causes worldwide concern.Successively held the meeting of 4 international seal chinaberrys in 1980～1994 years.Domestic existing multiple be that the insecticide of Main Ingredients and Appearance occurs with the nimbin, as Chinese patent disclosed 99114796.0,00114227.5; Also have obtaining of some nimbins or its missible oil product that is mixed to register and be extensive use of.But because of in the molecular structure of nimbin, having the active α hydrogen atom and the ring strain of unsaturated bond, ehter bond, carbonyl, nimbin is degraded fast under UV-irradiation and under the conditions such as water, oxygen, high temperature, is unfavorable for the preservation of agricultural chemicals and to the control of insect.Water insoluble because of nimbin in addition, generally need make the missible oil use by adding organic solvent, the influence of the environment that a large amount of consumptions of organic solvent and solvent evaporates are brought has to be solved.
Technology contents
The objective of the invention is to propose a kind of inclusion compound and preparation method thereof of cyclodextrin or derivatives thereof of nimbin, to improve the nimbin insecticide to ultraviolet light, to the stability of heat, prolong the lasting period of insecticide, simultaneously, improve the solvability of the nimbin insecticide that is insoluble in water to a certain extent.
The present invention is the inclusion compound of a kind of nimbin 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, nimbin are the inclusion compound of guest molecule to the molecule of nimbin by inclusion.Wherein, the molecular proportion of nimbin and cyclodextrin or cyclodextrine derivatives is 1: 2, and promptly a nimbin molecule is by two cyclodextrin moleculars or two cyclodextrine derivatives molecule institute inclusions.
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), any in the 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 nimbin and cyclodextrin or cyclodextrine derivatives, and by coprecipitation, solid reaction process reaction, the cyclodextrin inclusion of generation nimbin.Described co-precipitation preparation method is, cyclodextrin is placed reactor and is heated to more than 50 ℃ make saturated aqueous solution, be the derivative 1 of cyclodextrin or cyclodextrin with the nimbin amount of substance of organic solvent dissolution: the 1-8 amount of substance nimbin solution, 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, the preparation method is, be dried to constant weight with twice recrystallization of raw material of the derivative 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 nimbin amount of substance and be half of derivative amount of substance of cyclodextrin or cyclodextrin, nimbin is dissolved in the organic solvent, at N
2Or H
2Or CO
2Solution with nimbin 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 nimbin 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 nimbin or cyclodextrin.For preparing the inclusion compound of analytically pure nimbin, can be recrystallized to above-mentioned chemical pure inclusion compound, silicagel column separates or high performance liquid preparative chromatography separates and vacuum drying.
The inclusion compound preparation method of a kind of cyclodextrin of nimbin and cyclodextrine derivatives is characterized in that described solid phase preparation method is, the derivative of cyclodextrin or cyclodextrin is mixed with nimbin, 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 60 ± 20 ℃ scope in of protection is placed in the vacuum drying chamber more than the dry 4h again, gets the cyclodextrin of nimbin and the inclusion compound of cyclodextrine derivatives; Wash to remove unreacted nimbin 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 nimbin 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 nimbin and the inclusion compound of cyclodextrine derivatives.
In the solid reaction process of nimbin and cyclodextrin and cyclodextrine derivatives, nimbin is 1 with the amount of substance ratio of cyclodextrin in the reactant: 1-8, and wherein best ratio is 1: 2, this is the molecular proportion of its inclusion compound just.On this ratio, nimbin obtains effective inclusion, and cyclodextrin is not waste also.
Beneficial effect
The beneficial effect that is brought after the invention process is: after the derivative of nimbin and cyclodextrin or cyclodextrin forms inclusion compound, because the branch ascus of cyclodextrin has been wrapped up nimbin on molecular level, degraded modes such as the illumination degrading that cyclodextrin has been avoided nimbin to the sterically hindered effect and the complexing of vegetable insecticide, hydrolysis, polymerization, oxidation, strengthened the stability of nimbin, the corresponding lasting period that prolongs insecticide.
Because the hydrophilic hydroxyl that much is in the molecule exocoel is arranged in the cyclodextrin molecular, for hydrophobic for the nimbin of utmost point low-solubility in the water, after its molecule entered the hydrophobicity inner chamber of cyclodextrin, nimbin was by means of cyclodextrin hydrophily shell, and its water-soluble significantly increases.If used the fabulous 2-hydroxypropyl of dissolubility, 2, cyclodextrine derivatives such as 6-dimethyl-beta cyclodextrin, the raising of the solvability of nimbin in water is more remarkable, and this has also relatively increased the interior absorption of nimbin.
Experimental result by the nimbin 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 nimbin and cyclodextrin inclusion compound thereof shows, shine nimbin 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 nimbin 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 nimbin 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 nimbin Hp-β-CYD inclusion compound of nimbin nimbin | ????215 ????215 ????215 | ???40 ???40 ???40 | ??22.4 ??32.1 ??31.3 | ??13.3 ??31.5 ??26.3 | ??4.5 ??26.4 ??24.0 | ??2.6 ??18.2 ??17.4 |
The heat endurance of inclusion compound also is significantly increased, the Benexate Hydrochloride of the nimbin of sealing (adding small amount of acetone for increasing its solvability), nimbin, the aqueous solution of nimbin Hp-Benexate Hydrochloride 40 μ m are respectively 55 ℃ of heating 14 days, the aqueous solution of nimbin is reduced to 0 μ M from 40 μ M, and the Benexate Hydrochloride of nimbin is reduced to degraded to the 11.7 μ M of 15.9 μ M, the nimbin 2-hydroxy propyl-Beta cyclodextrin inclusion compound aqueous solution.After forming inclusion compound, cyclodextrin has effectively prevented the degraded of nimbin.
The present invention has also improved the solvability of vegetable insecticide nimbin effectively, nimbin 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 nimbin improve 26 times, with the cyclodextrin encapsulated nimbin of 2-hydroxy propyl-Beta the content of nimbin 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 Ingredients and Appearance also is feasible with the cyclodextrin inclusion compound of nimbin.
Compare with nimbin, after nimbin is subjected to cyclodextrin inclusion compound, its biologically active there is certain influence, with Agricultural University Of South China's insect toxicological study chamber development, 0.3% nimbin emulsion of being produced by Shenzhen's farming Bao Bio-Engineering Company is for trying with reference to medicament, is cabbage heart for studying thing.Controlling object is a diamond-back moth.The test method test is taked to distinguish at random group and is arranged, 4 repetitions, every sub-district area 20m
21000 times of liquid of nimbin emulsion are established in test, the Benexate Hydrochloride of nimbin, nimbin 2-hydroxy propyl-Beta cyclodextrin and 4 processing of clear water contrast.Use workers and peasants' 16 type knapsack sprayers, by the amount of liquid medicine even spraying of per hectare 750kg, the clear water of check plot spray equivalent.Investigation insect population number before the dispenser, 3d, 7d, 15d, 21d adopt the 5 point samplings record borer population of living after dispenser, and calculate insect population go down rate and control efficiency.Result and analytical test the results are shown in Table 2
The solution of the inclusion compound of table 2 nimbin and beta-schardinger dextrin-thereof is to the preventive effect experiment of diamond-back moth.
| The beta-CD inclusion nimbin Hp-β of azadirachtin insecticide and 1000 times of nimbins of inclusion compound nimbin thereof-CYD inclusion compound CK | Concentration 10 -7M ? ? ??4 ? ??4 ??4 ? ? | Borer population 62 68 71 65 before the examination | 21d after the 15d dispenser after the 7d dispenser after the 3d dispenser after the dispenser |
| The preventive effect that the goes down preventive effect preventive effect anti-efficient % % that goes down that goes down that goes down leads % % and leads % % and lead % % 78.1 79.0 89.8 91.6 72.4 87.6 66.4 77.3 63.5 65 83.6 86.6 85.1 88.7 76.2 84.0 70.1 71.4 82.7 85.8 86.9 90.3 73.2 82.1-4.4-22.1-31.5-48.5 |
Nimbin with molar concentration is compared with its inclusion compound activity, and the nimbin effect is slightly high when 3d and 7d, and the inclusion compound preventive effect is higher constantly at 5d and 21d, and this may form the decomposition that reduces the nimbin of knowing clearly behind the inclusion compound with nimbin, and it is relevant to have prolonged the longevity of residure.
The invention example
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 nimbin:
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 nimbin 5ml dissolve with methanol, be added to dropping funel, under stirring condition, dropwise 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 nimbin-cyclodextrin inclusion compound, nimbin is 1: 2 with the ratio of the amount of substance of beta-schardinger dextrin-in its inclusion compound, and product is a white powder.
Example 2 is prepared the inclusion compound of its corresponding beta-schardinger dextrin-by seal chinaberry dry powder
Get the beta cyclodextrin of 0.03mol, place three-neck flask, the water that adds 150ml is stirred to evenly, adds 150ml water heated and stirred to beta-schardinger dextrin-and all dissolves, and continues to be warming up to 70 ℃, feeds N in three-neck flask
2Not oxidized with the protective reaction thing; accurately take by weighing seal chinaberry dry powder 30 grams that contain nimbin 10%; dissolve with methanol with 300ml; be added to dropping funel; under stirring condition, dropwise splash in the flask that beta-schardinger dextrin-is housed; continue to stir 8 hours; solution is concentrated into 60ml under vacuum condition; after cooling to room temperature; placing 4 ℃ of refrigerations spends the night; filter out precipitation, the inclusion compound that obtains add the OP-10 of 60ml and the neopelex surfactant of 40g, add an amount of cosolvent; stabilizing agent and thin up promptly get 0.34% micro nimbin emulsion to 1000ml.Can be used for preventing and treating paddy rice, vegetables and fruit tree pest insect.Its insect protected spectrum but lasting period identical with nimbin prolongs at double.
The solid reaction process preparation of the inclusion compound of the HP-beta cyclodextrin of example 3 nimbins.
Get the HP-beta cyclodextrin (adlreach) of 0.01mol, the water that adds 10ml is stirred to evenly, accurately takes by weighing nimbin 0.005mol, grinds 2h jointly with the HP-beta cyclodextrin, 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 60 ℃ of 4h again; Cooling, add in the ethanol flush away product of 5ml the not nimbin of inclusion, 60 ℃ of washings with 10ml remove unreacted nimbin again, for obtaining more highly purified inclusion compound, inclusion compound can be dissolved in water, heating, with recrystallization method recrystallization twice,, last vacuum drying, can get purity and surpass 98% inclusion compound, in the inclusion compound in the molecule ratio of nimbin and the amount of substance of HP-beta cyclodextrin be 1: 2.
Claims (6)
1, the inclusion compound of a kind of nimbin cyclodextrin or cyclodextrine derivatives, it is characterized in that, the molecule of nimbin by inclusion in the cavity of the derivative of cyclodextrin or cyclodextrin, formation is that host molecule, nimbin are the inclusion compound of guest molecule with the cyclodextrin, wherein, the molecular proportion of nimbin and cyclodextrin or cyclodextrine derivatives is 1: 2, and promptly a nimbin molecule is by two cyclodextrin moleculars or two cyclodextrine derivatives molecule institute inclusions.
2, the inclusion compound of nimbin cyclodextrin according to claim 1 or cyclodextrine derivatives, the derivative that it is characterized in that cyclodextrin 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-CDY), in the glucosyl group cyclodextrin any.
3, the preparation method of the inclusion compound of a kind of nimbin cyclodextrin or cyclodextrine derivatives, it is characterized in that, cyclodextrin placed reactor and be heated to more than 50 ℃ make saturated aqueous solution, with the nimbin amount of substance of organic solvent dissolution is 1: 1/8 nimbin solution of cyclodextrin amount of substance, 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.
4, the preparation method of the inclusion compound of a kind of nimbin cyclodextrin or cyclodextrine derivatives, it is characterized in that, be dried to constant weight with twice recrystallization of raw material of the derivative 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 nimbin amount of substance and be half of derivative amount of substance of cyclodextrin or cyclodextrin, nimbin is dissolved in the organic solvent, at N
2Or H
2Or CO
2Solution with nimbin under the protection of gas slowly adds in the reactor; described organic solvent is acetone or ether; methyl alcohol; ethanol; propyl alcohol; pyridine; DMF; a kind of in 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; with unreacted nimbin in a small amount of organic solvent eccysis filter residue; only remove unreacted cyclodextrin in the filter residue with a spot of washing again; the inclusion compound of the derivative of dry cyclodextrin that promptly obtains nimbin or cyclodextrin; for preparing the inclusion compound of analytically pure nimbin, can be recrystallized to above-mentioned chemical pure inclusion compound; silicagel column separates or high performance liquid preparative chromatography separates and vacuum drying.
5, the inclusion compound preparation method of a kind of cyclodextrin of nimbin and cyclodextrine derivatives is characterized in that, the derivative of cyclodextrin or cyclodextrin is mixed with nimbin, 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 60 ± 20 ℃ scope in of protection is placed in the vacuum drying chamber more than the dry 4h again, gets the cyclodextrin of nimbin and the inclusion compound of cyclodextrine derivatives; , remove unreacted cyclodextrin with Warm Wash again and get the cyclodextrin of chemical pure nimbin and the inclusion compound of cyclodextrine derivatives to remove unreacted nimbin in the inclusion compound with ethanol or acetone organic solvent washing; 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 nimbin and the inclusion compound of cyclodextrine derivatives.
6. the cyclodextrin of nimbin according to claim 5 or cyclodextrin derivant clathrate method for making is characterized in that, nimbin is 1 with the ratio of the amount of substance of cyclodextrin in the reactant: 1-8.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112911934A (en) * | 2018-10-24 | 2021-06-04 | 阿达玛马克西姆有限公司 | Use of cyclodextrins as agrochemical delivery systems |
| CN113481726A (en) * | 2021-07-28 | 2021-10-08 | 爱慕股份有限公司 | Preparation method of botanical anti-mosquito textile fabric |
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2002
- 2002-12-25 CN CN 02149738 patent/CN1425293A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112911934A (en) * | 2018-10-24 | 2021-06-04 | 阿达玛马克西姆有限公司 | Use of cyclodextrins as agrochemical delivery systems |
| CN113481726A (en) * | 2021-07-28 | 2021-10-08 | 爱慕股份有限公司 | Preparation method of botanical anti-mosquito textile fabric |
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