CN1202717C - Alpha-ternary thiophene cyclo-dextrin or cyclo-dextrin biological clathrate and preparing method - Google Patents
Alpha-ternary thiophene cyclo-dextrin or cyclo-dextrin biological clathrate and preparing method Download PDFInfo
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- CN1202717C CN1202717C CN 02149735 CN02149735A CN1202717C CN 1202717 C CN1202717 C CN 1202717C CN 02149735 CN02149735 CN 02149735 CN 02149735 A CN02149735 A CN 02149735A CN 1202717 C CN1202717 C CN 1202717C
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Abstract
The present invention belongs to the field of pesticides, particularly to cyclodextrin of plant pesticides, an inclusion compound of derivatives thereof and a preparation method thereof. The present invention prepares the inclusion compound of cyclodextrin of alpha-terthienyl or derivatives thereof from carrying out reactions on alpha-terthienyl and cyclodextrin or derivatives thereof by using a coprecipitation method and asolid reaction method, and after the inclusion compound of alpha-terthienyl is formed, the steric hindrance and the complexation of the cyclodextrin protect the alpha-terthienyl in the cavity; the rate of degradation reactions of the alpha-terthienyl is decreased, and the pesticide becomes stable; simultaneously a plurality of hydroxyl groups outside the cavity of the cyclodextrin are helpful to increase the dissolvability under water of the alpha-terthienyl in the cavity, and compared with the alpha-terthienyl, the inclusion compound of the cyclodextrin of the alpha-terthienyl or the derivatives of the cyclodextrin, which is obtained in the present invention, has a longer effect keeping 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.α-terthienyl ([2,2 ', 5 ' 2 "] Terthiophene; or be called for short a kind of active insecticidal components of α-T); it is a kind of important photoactivation insecticide; its mechanism of action is that α-terthienyl is activated under the irradiation of light; produce strong oxidizing property materials such as singlet oxygen, peroxide, superoxides, hydroxyl radical free radical with materials such as water, oxygen for from plants such as Aztec marigold, extracting, thereby to material oxidations such as the cell membrane of insect, mitochondrial DNA, superoxide dismutase, superoxide dismutases.The insecticidal activity of this insecticide under illumination is more than 40 times of dark.But because of the activation process of α-terthienyl also is degradation process, α-terthienyl is degraded fast under UV-irradiation and under the conditions such as water, oxygen, high temperature, makes the very fast inefficacy of this insecticide, is unfavorable for the preservation of agricultural chemicals and to the control of insect.Water insoluble because of α-terthienyl 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.
Summary of the invention
The objective of the invention is to propose a kind of preparation method of inclusion compound of cyclodextrin or derivatives thereof of α-terthienyl, to improve α-terthienyl insecticide to ultraviolet light, to the stability of heat, prolong the lasting period of insecticide, simultaneously, improve the solvability of the α-terthienyl insecticide that is insoluble in water to a certain extent.
The present invention is the inclusion compound of a kind of α-terthienyl 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, α-terthienyl are the inclusion compound of guest molecule to the molecule of α-terthienyl by inclusion.Wherein, the molecular proportion of α-terthienyl and cyclodextrin or cyclodextrine derivatives is 1: 2, and promptly a α-terthienyl 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 α-terthienyl and cyclodextrin or cyclodextrine derivatives, and by coprecipitation, solid reaction process reaction, the cyclodextrin inclusion of generation α-terthienyl.Described co-precipitation preparation method is, cyclodextrin placed reactor and is heated to more than 50 ℃ make saturated aqueous solution, and be α-terthienyl solution of the 1-1/8 of cyclodextrin amount of substance with the α-terthienyl 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 α-terthienyl amount of substance and be half of derivative amount of substance of cyclodextrin or cyclodextrin, α-terthienyl is dissolved in the organic solvent, at N
2Or H
2Or CO
2Solution with α-terthienyl under the protection of gas slowly adds in the reactor; described organic solvent is any in acetone, 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 α-terthienyl 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 α-terthienyl or cyclodextrin.For preparing the inclusion compound of analytically pure α-terthienyl, 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 preparation method is, the derivative of cyclodextrin or cyclodextrin is mixed with α-terthienyl, 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 α-terthienyl and the inclusion compound of cyclodextrine derivatives; Wash to remove unreacted α-terthienyl 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 α-terthienyl 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 α-terthienyl and the inclusion compound of cyclodextrine derivatives.
In the solid reaction process of α-terthienyl and cyclodextrin and cyclodextrine derivatives, the mol ratio of α-terthienyl and cyclodextrin is 1 :～8 in the reactant, and wherein best ratio is 1: 2, and this is the molecular proportion of its inclusion compound just.On this ratio, α-terthienyl 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 α-terthienyl and cyclodextrin or cyclodextrin forms inclusion compound, because of the branch ascus of cyclodextrin has been wrapped up vegetable insecticide on molecular level, degraded modes such as the illumination degrading that cyclodextrin has been avoided α-terthienyl to the sterically hindered effect and the complexing of α-terthienyl, hydrolysis, polymerization, oxidation, strengthened the stability of vegetable insecticide, the corresponding lasting period that prolongs insecticide.After the inclusion compound of α-terthienyl is taken in by insect, be easy to be degraded as the cyclodextrin of polysaccharide by insect, α-terthienyl is released, and then plays insecticidal action.
The hydrophilic hydroxyl that much is in the molecule exocoel is arranged because of cyclodextrin molecular, for hydrophobic for the α-terthienyl of utmost point low-solubility in the water, after its molecule enters the hydrophobicity inner chamber of cyclodextrin, α-terthienyl is 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 α-terthienyl in water is more remarkable, and this has also relatively increased the solvability of α-terthienyl.
Experimental result by the part vegetable insecticide 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 α-terthienyl and cyclodextrin inclusion compound thereof shows, uviol lamp with 2 parallel 30W shines 40 μ M α-terthienyl and inclusion compounds thereof simultaneously, 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 α-terthienyl 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 α-terthienyl and beta-schardinger dextrin-thereof under the UV-irradiation of different time.
Measure wavelength residual concentration (μ M)
Insecticide and inclusion compound thereof
Nm 0 hour 6 hours 12 hours 18 hours 24 hours
(α-T) 315 40 12.5 4.6 1.8 0.66 for α-terthienyl
The Benexate Hydrochloride 315 40 38.6 37.3 36.0 34.2 of α-T
α-T2-hydroxy propyl-Beta is cyclodextrin encapsulated
315 40 37.7 34.5 31.6 28.0
Thing
The heat endurance of inclusion compound also is significantly increased, the Benexate Hydrochloride of the α-terthienyl of sealing (adding small amount of acetone for increasing its solvability), α-terthienyl, the aqueous solution of α-terthienyl 2-hydroxy propyl-Beta cyclodextrin inclusion compound 40 μ m are respectively 54 ± 2 ℃ of heating 14 days, except that the aqueous solution of α-terthienyl from 40 μ M reduce to 38.2 μ M, the degraded of the Benexate Hydrochloride of α-terthienyl, α-terthienyl 2-hydroxy propyl-Beta cyclodextrin inclusion compound aqueous solution is all not obvious.
The present invention has also improved the solvability of vegetable insecticide α-terthienyl effectively, α-terthienyl 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 α-terthienyl improve 52 times, with the cyclodextrin encapsulated α-terthienyl of 2-hydroxy propyl-Beta the content of α-terthienyl in the aqueous solution is reached more than 3.5%.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 α-terthienyl.
Compare with α-terthienyl, after α-terthienyl is subjected to cyclodextrin inclusion compound, biologically active is subjected to 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 α-terthienyl of the respective concentration that 0.5ml has been made into and the cyclodextrin inclusion compound solution or the suspension of α-terthienyl 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 α-terthienyl and beta-schardinger dextrin-thereof is to the killing action of pine wood nematode.
α-terthienyl (remaining pine wood nematode number (head) of the insecticide concentration of α-T)
And inclusion compound μ M tried preceding 24 hours 48 hours 72 hours 96 hours
α-T 2.5 100 61 27 3 0
The Benexate Hydrochloride 2.5 100 84 53 14 5 of α-T
The 2-hydroxy propyl-Beta cyclodextrin bag of α-T
2.5 100 71 42 29 2
Compound
α-T 25 100 46 18 2 0
The Benexate Hydrochloride 25 100 32 10 61 of α-T
α-T2-hydroxy propyl-Beta cyclodextrin bag
25 100 41 22 18 3
Compound
α-T 25 100 91 67 30 32 behind the UV 12h
The β of α-T behind the UV 12h-ring is stuck with paste
25 100 53 24 18 4
The spermatophore compound
α behind the UV 12h-T2-hydroxyl
25 100 62 30 13 6
Propyl group-beta cyclodextrin clathrate
CK 100 104 109 113 121
α-terthienyl with molar concentration is compared with its inclusion compound activity, α when 2.5 μ M-terthienyl effect is slightly high, the inclusion compound activity is higher when 25 μ M, and this has increased solvability after may forming inclusion compound with α-terthienyl, and the transport properties that has improved in the drug line polypide is relevant.
In addition, as α-T, the Benexate Hydrochloride of α-T, after the 2-hydroxy propyl-Beta cyclodextrin inclusion compound of α-T all passes through the ultraviolet irradiation of 12h, because of α-T at ultraviolet ray and oxygen, the effect of water is decomposed down fast, the sharp sharp fall of concentration is low, and the Benexate Hydrochloride of α-T, α-T in the 2-hydroxy propyl-Beta cyclodextrin inclusion compound of α-T has avoided contacting with the direct of oxygen because of the insulating effect of cyclodextrin, concentration reduces little, to the killing effect of pine wood nematode, the Benexate Hydrochloride of α-T, the 2-hydroxy propyl-Beta cyclodextrin inclusion compound of α-T will be higher than α-T far away.
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 α-terthienyl:
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 α-terthienyl 5ml acetone solution, put into 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 α-terthienyl-cyclodextrin inclusion compound, its inclusion compound mol ratio beta-schardinger dextrin-: α-terthienyl 2: 1, product is a pale yellow powder, the ratio of this pale yellow powder of 10g with 1: 5000 added water and add surfactant OP-10 20g, can get the stable milk-white coloured suspension of α-terthienyl-cyclodextrin inclusion compound of 50 kilograms.Can be used for killing mosquito larvae and other insect.This pale yellow powder of 10g ratio with 1: 50 is added water and adds 0P-10 surfactant 50ml and neopelex 40g, add microemulsion that propyl alcohol 200ml and stabilizing agent make and can be injected to and be used for the treatment of the disease tree that suffers from pine wood nematode in the pine tree.
The solid reaction process preparation of the inclusion compound of the HP-beta cyclodextrin of example 2 α-terthienyl.Get the HP-beta cyclodextrin (adlrich) of 0.01mol, the water that adds 10ml is stirred to evenly, and α-terthienyl 0.005mol grinds 2h with the HP-beta cyclodextrin, jointly 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 α-terthienyl of inclusion, removing unreacted α-terthienyl with 60 ℃ of washings of 10ml again is to obtain 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 95% inclusion compound, in the inclusion compound in the molecule ratio of α-terthienyl and the amount of substance of HP-beta cyclodextrin be 1: 2.
Claims (5)
1, the inclusion compound of a kind of α-terthienyl cyclodextrin or cyclodextrine derivatives, it is characterized in that, the molecule of α-terthienyl by inclusion in the cavity of the derivative of cyclodextrin or cyclodextrin, formation is host molecule with the derivative of cyclodextrin or cyclodextrin, α-terthienyl is the inclusion compound of guest molecule, wherein, the molecular proportion of α-terthienyl and cyclodextrin or cyclodextrine derivatives is 1: 2, promptly a α-terthienyl 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 α-terthienyl 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 α-terthienyl amount of substance of organic solvent dissolution be cyclodextrin or cyclodextrin the derivative amount of substance 1: the α of 1-8-terthienyl solution, 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; wherein; the molecular proportion of the inclusion compound of described α-terthienyl and cyclodextrin or cyclodextrine derivatives is 1: 2; promptly a α-terthienyl 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 α-terthienyl 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 α-terthienyl amount of substance and be half of derivative amount of substance of cyclodextrin or cyclodextrin, α-terthienyl is dissolved in the organic solvent, at N
2Or H
2Or CO
2Solution with α-terthienyl 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 α-terthienyl 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 α-terthienyl or cyclodextrin; for preparing the inclusion compound of analytically pure α-terthienyl; can be recrystallized to above-mentioned chemical pure inclusion compound; silicagel column separates or high performance liquid preparative chromatography separates and vacuum drying; wherein; the molecular proportion of the inclusion compound of described α-terthienyl and cyclodextrin or cyclodextrine derivatives is 1: 2; promptly a α-terthienyl 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 α-terthienyl or cyclodextrine derivatives, it is characterized in that described solid phase preparation method is, the derivative of cyclodextrin or cyclodextrin is mixed with α-terthienyl, add 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 dryly more than 4 hours again, gets the cyclodextrin of α-terthienyl or the inclusion compound of cyclodextrine derivatives; To remove unreacted α-terthienyl in the inclusion compound, remove unreacted cyclodextrin with Warm Wash again or cyclodextrine derivatives gets the cyclodextrin of chemical pure α-terthienyl or the inclusion compound of cyclodextrine derivatives with organic solvent 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 α-terthienyl or the inclusion compound of cyclodextrine derivatives, wherein, the molecular proportion of the inclusion compound of described α-terthienyl and cyclodextrin or cyclodextrine derivatives is 1: 2, promptly a α-terthienyl 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 α-terthienyl according to claim 4 or cyclodextrin derivant clathrate method for making is characterized in that, α-terthienyl is 1 with the ratio of the amount of substance of cyclodextrin in the reactant: 1-8.
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