CN104402954A - Methylaminoavermectin monosaccharide compound and preparing method and application thereof - Google Patents
Methylaminoavermectin monosaccharide compound and preparing method and application thereof Download PDFInfo
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- CN104402954A CN104402954A CN201410706436.2A CN201410706436A CN104402954A CN 104402954 A CN104402954 A CN 104402954A CN 201410706436 A CN201410706436 A CN 201410706436A CN 104402954 A CN104402954 A CN 104402954A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H17/00—Compounds containing heterocyclic radicals directly attached to hetero atoms of saccharide radicals
- C07H17/04—Heterocyclic radicals containing only oxygen as ring hetero atoms
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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Abstract
The invention relates to the technical field of insecticidal farm chemicals, in particular to a methylaminoavermectin monosaccharide compound and a preparing method and application thereof. The methylaminoavermectin monosaccharide compound is obtained through the further chemical modification of monosaccharide formed by abamectin desugaring. Compared with a common abamectin product, the use of the methylaminoavermectin monosaccharide compound prepared by the invention as an insecticide has the characteristics of high insecticidal effect, wide insecticidal spectrum, great lasting effect, no residue, no pollution and the like. Particularly, the problem that insects, such as cotton aphid, have drug resistance to the existing insecticide is effectively solved, the damage fetal insecticide effect is remarkable, and the methylaminoavermectin monosaccharide compound is suitable for being popularized and applied in related fields.
Description
Technical field
The present invention relates to desinsection technical field of pesticide, particularly relate to methylaminoabamectin monosaccharide compounds and its production and use.
Background technology
Avrmectin (Avermectin, be called for short AVM) be a kind of low toxicity, efficient, high selection, green, environment-friendly type and biogenic sterilant, it efficiently solves height poison, resistance and the problem to environmental effects that traditional agricultural chemicals exists, thus obtains emphasis and applies.But along with the universal of Avrmectin in recent years and derived product thereof with promote, its resistance is also more and more obvious, add the thermal destruction of Avrmectin own and photodegradation is very serious, the lasting period shortens, also more and more less compared to the advantage of other chemical pesticides.
Therefore, the new Avrmectin derived product of research and development is needed badly to overcome the defect of currently available products.
Summary of the invention
The object of the invention is, for prior art Problems existing, provide a kind of methylaminoabamectin monosaccharide compounds and its production and use.
The technical scheme that the present invention deals with problems is: a kind of methylaminoabamectin monosaccharide compounds, has structural formula shown in following formula I:
In formula, X-Y is-CH=CH-or-CH
2cH (OH)-.
Present invention also offers the preparation method of above-mentioned methylaminoabamectin monosaccharide compounds, comprise the steps:
(1) in the reactor, with organic solvent, avermectin monosaccharide is dissolved, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 DEG C ~-15 DEG C, successively drips protective material and acid binding agent successively, continue stirring reaction more than 15 minutes;
(3) in step (2) gained material, add acid binding agent, oxygenant successively, continue stirring reaction more than 15 minutes;
(4) to acid adding termination reaction, then stratification in step (3) gained material; Then gained organic phase sodium bicarbonate aqueous solution is extracted again, then secondary clearing; Then, the organic phase underpressure distillation obtained will be separated after layering, dry;
(5) by dry for step (4) products obtained therefrom organic solvent dissolution, after being warming up to 50 DEG C ~ 60 DEG C, add heptamethyldisilazane and catalyzer successively, react more than 4 hours;
(6) step (5) gained material is cooled to-10 DEG C to-15 DEG C, then, adds methyl alcohol, then add sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reaction more than 15min;
(7) in step (6) gained material, add catalyzer, then add sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reacts more than 2 hours; Then, in reaction solution, acid adding stops, and adjusts pH=6 ~ 6.5, then, adds adjusting PH with base=7 ~ 7.5, extracted by the isopyknic water of separating obtained organic phase after stratification, then, by organic phase precipitation/drying, obtain methylaminoabamectin monosaccharide compounds.
Preferably, in the preparation method of methylaminoabamectin monosaccharide compounds of the present invention, in described step (3), after adding oxygenant, also add pro-oxidant; Described pro-oxidant is solid phosgene, and the mass ratio of avermectin monosaccharide and promotor is 2:1 to 3:1.
Preferably, in the preparation method of methylaminoabamectin monosaccharide compounds of the present invention, described avermectin monosaccharide is Avrmectin B
1amonose or Avrmectin B
2amonose.
Preferably, state in the preparation method of methylaminoabamectin monosaccharide compounds on the invention, the temperature of reaction of described step (2) controls at-18 DEG C to-22 DEG C; The temperature of reaction of described step (3) controls at-17 DEG C to-23 DEG C.
Preferably, in the preparation method of methylaminoabamectin monosaccharide compounds of the present invention, in described step (1), described organic solvent is methylene dichloride, and the mass ratio of avermectin monosaccharide and methylene dichloride is 1:6 to 1:4; In described step (2), described protective material is allyl chlorocarbonate, described acid binding agent is Tetramethyl Ethylene Diamine, and the mass ratio of avermectin monosaccharide and allyl chlorocarbonate is 7:1 to 10:1, and the mass ratio of avermectin monosaccharide and Tetramethyl Ethylene Diamine is 4:1 to 6:1; In described step (3), described acid binding agent is Tetramethyl Ethylene Diamine, described oxygenant is dimethyl sulfoxide (DMSO), the mass ratio 4:1 to 5:1 of avermectin monosaccharide and Tetramethyl Ethylene Diamine, and the mass ratio of avermectin monosaccharide and dimethyl sulfoxide (DMSO) is 5:1 to 7:1; In described step (4), for termination reaction is phosphoric acid solution to institute's acid adding in step (3) gained material, the mass ratio of phosphoric acid solution used and methylene dichloride is 1:1, and the mass ratio of sodium bicarbonate aqueous solution and methylene dichloride is 1:1; In described step (5), described organic solvent is ethylene dichloride, described catalyzer is trifluoroacetic acid zinc, the mass ratio of avermectin monosaccharide and ethylene dichloride is 1:5 to 1:4, the mass ratio of avermectin monosaccharide and heptamethyldisilazane is 2:1, and the mass ratio of avermectin monosaccharide and trifluoroacetic acid zinc is 2:1; In described step (6), the mass ratio of avermectin monosaccharide and methyl alcohol is 1:1, and the mass ratio of avermectin monosaccharide and sodium borohydride is 15:1 to 20:1; In described step (7), termination reaction acid used is acetic acid, adjusts pH alkali used to be ammoniacal liquor; Described catalyzer is tetrakis triphenylphosphine palladium, and the mass ratio of avermectin monosaccharide and tetrakis triphenylphosphine palladium is 600:1, and the mass ratio of avermectin monosaccharide and sodium borohydride is 30:1.
Preferably, in the preparation method of methylaminoabamectin monosaccharide compounds of the present invention, in described step (1) and (5), organic solvent used is 1,2-ethylene dichloride.
Preferably, in the preparation method of methylaminoabamectin monosaccharide compounds of the present invention, in described step (4), the mass percent concentration of termination reaction phosphoric acid solution used is 2%, and described sodium bicarbonate aqueous solution is saturated solution; In described step (7), the mass percent concentration of acetic acid added by termination reaction is 12%, and adjust pH alkali used to be ammoniacal liquor, the mass percent concentration of ammoniacal liquor is 20%.
Preferably, in the preparation method of methylaminoabamectin monosaccharide compounds of the present invention, in step (6) and (7), when adding sodium borohydride, reaction is fierce, and temperature variation is large, need control feed rate, slowly add, control feed rate and be preferably 0.3g/min ~ 0.5g/min.
Preferably, in the preparation method of methylaminoabamectin monosaccharide compounds of the present invention, described avermectin monosaccharide has structural formula shown in following formula II:
Formula II
In formula, Z-W is-CH=CH-or-CH
2-CHOH-.
Avrmectin B
1amonose or Avrmectin B
2apreparation method's step of monose is as follows:
(1) in the reactor, with organic solvent, Avrmectin is dissolved, obtain abamectin solution; Described organic solvent is preferably tetrahydrofuran (THF), is added by Avrmectin in tetrahydrofuran (THF) after stirring and dissolving, and gained abamectin solution subcooling recycle pump is cooled to-10 DEG C ~ 0 DEG C; The mass ratio of Avrmectin and tetrahydrofuran (THF) is preferably 1:6 ~ 1:10;
(2) in step (1) gained abamectin solution, slowly drip sulphuric acid soln, keep-10 DEG C ~ 0 DEG C to react 2 hours ~ 2.5 hours, then temperature of reaction is risen to 33 DEG C ~ 37 DEG C, continue reaction 48 hours ~ 54 hours; Before this, first with subcooling recycle pump, the sulphuric acid soln of preparation is cooled to-10 DEG C ~ 0 DEG C, during dropping, makes the temperature of described sulphuric acid soln be-10 DEG C ~ 0 DEG C, thus ensure that the temperature of itself and abamectin solution is consistent, and then reaction is evenly carried out; Drip sulphuric acid soln in step (1) gained abamectin solution after, in gained mixed reaction solution, the mass percentage of sulfuric acid is preferably 2% ~ 6%;
(3) after stopping step (2) reaction, after adjusting PH=7, stratification; Then gained organic phase is cleaned, then after secondary clearing, by being separated the organic phase evaporate to dryness obtained, obtain avermectin monosaccharide; Wherein, stopping step (2) reaction preferred mass percentage composition is the sodium hydroxide solution of 10%, for ensureing the high percentage extraction of organic phase, with saturated nacl aqueous solution, layering gained organic phase is cleaned, again after secondary clearing, by being separated the organic phase vacuum-drying obtained, obtain avermectin monosaccharide.
Present invention also offers the purposes of methylaminoabamectin monosaccharide compounds, described methylaminoabamectin monosaccharide compounds is as the activeconstituents of agricultural chemicals or auxiliary agent, preferably, as activeconstituents or the auxiliary agent of sterilant, compare with common Avrmectin product, insecticidal activity significantly improves, and insecticidal spectrum is wide, long-lasting is good, noresidue, nuisanceless, especially effective especially to cotton aphid.
Methylaminoabamectin monosaccharide compounds prepared by the present invention is at C by the monose of Avrmectin desugar formation
5by C on the basis of-OH protection
4the further chemical modification of-OH obtains.Methylaminoabamectin monosaccharide compounds prepared by the present invention adopts high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization, productive rate reaches more than 90%, and show in conjunction with its pesticidal applications effect analysis, compared with common Avrmectin product, it has that drug effect is high, insecticidal spectrum is wide, long-lasting is good, noresidue and the feature such as nuisanceless, especially the problem that cotton aphid class pest develops immunity to drugs to existing sterilant is efficiently solved, destroy lethality drug effect remarkable, be suitable for applying in association area.
Accompanying drawing explanation
Fig. 1 is the HPLC quantitative analysis spectrogram of the embodiment of the present invention 1 gained methylaminoabamectin B2a monose product;
Fig. 2 is the nuclear-magnetism NMR spectrogram of the embodiment of the present invention 1 gained methylaminoabamectin B2a monose product;
Fig. 3 is the HPLC quantitative analysis spectrogram of the embodiment of the present invention 2 gained methylaminoabamectin B1a monose product.
Embodiment
In the present invention, the methylaminoabamectin monosaccharide compounds provided, has structural formula shown in following formula I:
In formula, X-Y is-CH=CH-or-CH
2cH (OH)-.
The monosaccharide compounds of methylaminoabamectin shown in formula I building-up reactions formula is:
Wherein
be:
In formula, X-Y is-CH=CH-or-CH
2cH (OH)-.
In the present invention, the preparation method of methylaminoabamectin monosaccharide compounds performs following steps:
(1) in the reactor, with organic solvent, avermectin monosaccharide is dissolved, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 DEG C ~-15 DEG C, successively drips protective material and acid binding agent successively, continue stirring reaction more than 15 minutes;
(3) in step (2) gained material, add acid binding agent, oxygenant successively, continue stirring reaction more than 15 minutes;
(4) to acid adding termination reaction, then stratification in step (3) gained material; Then gained organic phase sodium bicarbonate aqueous solution is extracted again, then secondary clearing; Then, will the organic phase underpressure distillation obtained be separated, dry;
(5) by dry for step (4) products obtained therefrom organic solvent dissolution, after being warming up to 50 DEG C ~ 60 DEG C, add heptamethyldisilazane and catalyzer successively, react more than 4 hours;
(6) step (5) gained material is cooled to-10 DEG C to-15 DEG C, then, adds methyl alcohol, then add sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reaction more than 15min;
(7) in step (6) gained material, add catalyzer, then add sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reacts more than 2 hours; Then, in reaction solution, acid adding stops, and adjusts pH=6 ~ 6.5, then adds adjusting PH with base=7 ~ 7.5, extracted by the isopyknic water of separating obtained organic phase after stratification, then, by organic phase precipitation/drying, obtain methylaminoabamectin monosaccharide compounds.
State in the preparation method of methylaminoabamectin monosaccharide compounds on the invention, can react completely for ensureing and ensure speed of reaction, in described step (3), after adding oxygenant, also adding pro-oxidant; Described pro-oxidant is solid phosgene, and the mass ratio of avermectin monosaccharide and promotor is 2:1 to 3:1.
State in the preparation method of methylaminoabamectin monosaccharide compounds on the invention, by step (2) to the C of avermectin monosaccharide
5-OH protects, by step (3) to C
4-OH is oxidized, and realizes ammonification by step (5), carries out reduction reaction by step (6), by step (7) by C
5protection take off and realize deprotection; For ensureing that the product of serial reaction can realize smoothly, the temperature of reaction of described step (2) controls at-18 DEG C to-22 DEG C; The temperature of reaction of described step (3) controls at-17 DEG C to-23 DEG C; For making each highly effective reaction step by step obtain target product, preferably, in described step (1), described organic solvent is methylene dichloride, and the mass ratio of avermectin monosaccharide and methylene dichloride is 1:6 to 1:4; In described step (2), described protective material is allyl chlorocarbonate, described acid binding agent is Tetramethyl Ethylene Diamine, and the mass ratio of avermectin monosaccharide and allyl chlorocarbonate is 7:1 to 10:1, and the mass ratio of avermectin monosaccharide and Tetramethyl Ethylene Diamine is 4:1 to 6:1; In described step (3), described acid binding agent is Tetramethyl Ethylene Diamine, described oxygenant is dimethyl sulfoxide (DMSO), the mass ratio 4:1 to 5:1 of avermectin monosaccharide and Tetramethyl Ethylene Diamine, and the mass ratio of avermectin monosaccharide and dimethyl sulfoxide (DMSO) is 5:1 to 7:1; In described step (4), for termination reaction is phosphoric acid solution to institute's acid adding in step (3) gained material, the mass ratio of phosphoric acid solution used and methylene dichloride is 1:1, and the mass ratio of sodium bicarbonate aqueous solution and methylene dichloride is 1:1; In described step (5), described organic solvent is ethylene dichloride, described catalyzer is trifluoroacetic acid zinc, the mass ratio of avermectin monosaccharide and ethylene dichloride is 1:5 to 1:4, the mass ratio of avermectin monosaccharide and heptamethyldisilazane is 2:1, and the mass ratio of avermectin monosaccharide and trifluoroacetic acid zinc is 2:1; In described step (6), the mass ratio of avermectin monosaccharide and methyl alcohol is 1:1, and the mass ratio of avermectin monosaccharide and sodium borohydride is 15:1 to 20:1; In described step (7), termination reaction acid used is acetic acid, adjusts pH alkali used to be ammoniacal liquor; Described catalyzer is tetrakis triphenylphosphine palladium, and the mass ratio of avermectin monosaccharide and tetrakis triphenylphosphine palladium is 600:1, and the mass ratio of avermectin monosaccharide and sodium borohydride is 30:1.
State in the preparation method of methylaminoabamectin monosaccharide compounds on the invention, in described step (1) and (5), preferably, organic solvent used is the stability of 1,2-ethylene dichloride, effective guarantee reaction system.
State in the preparation method of methylaminoabamectin monosaccharide compounds on the invention, for effectively controlling product and the speed of response of reaction, in described step (4), the mass percent concentration of termination reaction phosphoric acid solution used is 2%; In described step (7), the mass percent concentration of acetic acid added by termination reaction is 12%; For ensureing extracting efficient, described in step (4), sodium bicarbonate aqueous solution is saturated solution, and adjust pH alkali used to be ammoniacal liquor in step (7), the mass percent concentration of ammoniacal liquor is 20%.
State in the preparation method of methylaminoabamectin monosaccharide compounds on the invention, react completely for ensureing, obtain the high yield of target product, in step (6) and (7), when adding sodium borohydride, reaction is fierce, temperature variation is large, must feed rate be controlled, slowly add, control feed rate and be preferably 0.3g/min ~ 0.5g/min.
State in the preparation method of methylaminoabamectin monosaccharide compounds on the invention, described avermectin monosaccharide has structural formula shown in following formula II:
Formula II
In formula, Z-W is-CH=CH-or-CH
2-CHOH-; Preparation method's step is as follows:
(1) in the reactor, with organic solvent, Avrmectin is dissolved, obtain abamectin solution; Described organic solvent is preferably tetrahydrofuran (THF), is added by Avrmectin in tetrahydrofuran (THF) after stirring and dissolving, and gained abamectin solution subcooling recycle pump is cooled to-10 DEG C ~ 0 DEG C; The mass ratio of Avrmectin and tetrahydrofuran (THF) is preferably 1:6 ~ 1:10;
(2) in step (1) gained abamectin solution, slowly drip sulphuric acid soln, keep-10 DEG C ~ 0 DEG C to react 2 hours ~ 2.5 hours, then temperature of reaction is risen to 33 DEG C ~ 37 DEG C, continue reaction 48 hours ~ 54 hours; Before this, first with subcooling recycle pump, the sulphuric acid soln of preparation is cooled to-10 DEG C ~ 0 DEG C, during dropping, makes the temperature of described sulphuric acid soln be-10 DEG C ~ 0 DEG C, thus ensure that the temperature of itself and abamectin solution is consistent, and then reaction is evenly carried out; Drip sulphuric acid soln in step (1) gained abamectin solution after, in gained mixed reaction solution, the mass percentage of sulfuric acid is preferably 2% ~ 6%;
(3) after stopping step (2) reaction, after adjusting PH=7, stratification; Then gained organic phase is cleaned, then after secondary clearing, by being separated the organic phase evaporate to dryness obtained, obtain avermectin monosaccharide; Wherein, stopping step (2) reaction preferred mass percentage composition is the sodium hydroxide solution of 10%, for ensureing the high percentage extraction of organic phase, with saturated nacl aqueous solution, separating obtained organic phase is cleaned, again after secondary clearing, by being separated the organic phase vacuum-drying obtained, obtain avermectin monosaccharide.
Preferably, described avermectin monosaccharide is Avrmectin B
1amonose or Avrmectin B
2amonose,
Methylaminoabamectin monosaccharide compounds prepared by the present invention adopts high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization.
In addition, present invention also offers the purposes of methylaminoabamectin monosaccharide compounds, as activeconstituents or the auxiliary agent of agricultural chemicals, preferably, as activeconstituents or the auxiliary agent of sterilant, compare with common Avrmectin product, insecticidal activity significantly improves, and insecticidal spectrum is wide, long-lasting is good, noresidue, nuisanceless, especially effective especially to cotton aphid, compensate for the resistance that this class pest produces existing sterilant.
Below in conjunction with specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to this.
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
Embodiment 1
Synthesize the methylaminoabamectin B2a monose as above shown in formula I, wherein, X-Y is-CH
2cH (OH)-, preparation method is as follows:
(1) take the avermectin B2a monose that 40g content is 90.9%, add 160g methylene dichloride, dissolve, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 ~-15 DEG C, successively drips 4.0g allyl chlorocarbonate and 6.7g Tetramethyl Ethylene Diamine successively, drip rear continuation stirring reaction 15 minutes;
(3) in the rear gained material of step (2) reaction, add 8g Tetramethyl Ethylene Diamine, 5.7g dimethyl sulfoxide (DMSO), 13.5g solid phosgene successively, drip rear continuation stirring reaction 15 minutes;
(4) to the phosphoric acid solution termination reaction of 200g2% in the rear gained material of step (3) reaction, stratification after stirring, then separating obtained organic phase 200g saturated sodium bicarbonate aqueous solution is extracted again, stratification, will be separated rear gained organic phase again in 55 DEG C of underpressure distillation, drying 2 hours;
(5) step (4) dry products obtained therefrom is joined 160g1, dissolve in 2-ethylene dichloride, the water-bath being placed in 50 DEG C heats, after temperature rises to 50 DEG C, add 20g heptamethyldisilazane and 20g catalyzer trifluoroacetic acid zinc successively, react 4 hours;
(6) gained material after step (5) reaction is cooled to-10 DEG C, then, add 40g methyl alcohol, more slowly add 2.0g sodium borohydride with 0.5g/min, temperature of reaction controls at-10 ~ 0 DEG C, continues reaction 15 minutes;
(7) in the rear gained material of step (6) reaction, add 0.067g catalyzer tetrakis triphenylphosphine palladium, more slowly add 1.33g sodium borohydride with 0.3g/min, temperature of reaction controls at-10 ~ 0 DEG C, reacts 2 hours; Then, by 12% acetic acid termination reaction, regulate pH to 6, then pH to 7.5 is regulated with 20% ammoniacal liquor, stratification, then extracts separating obtained organic phase water isopyknic with it once, stratification, in 55 DEG C of underpressure distillation, drying 2 hours, obtain the finished product methylaminoabamectin B2a monose that 28.3g content is 91.8%.
In the above-described embodiments, avermectin B2a monose used is as shown in formula II, and wherein, Z-W is-CH
2cH (OH)-, preparation method is as follows:
(1) 50g Avrmectin B is claimed
2a fine powder, adds 500g tetrahydrofuran solvent, stirs and makes it dissolve, and uses subcooling recycle pump that the temperature of solution is down to-10 DEG C ~ 0 DEG C simultaneously;
(2) in step (1) gained abamectin solution, the mass percentage of slowly dropping 0 DEG C ~ 10 DEG C is the 100g sulphuric acid soln of 30%, the whole dropping process time used is no less than half an hour, after dropping terminates, continue-10 DEG C ~ 0 DEG C reaction 2 hours, then reaction system is warming up to 37 DEG C, continues reaction 49 hours;
(3) treat that step (2) reaction terminates, be added drop-wise in reaction solution with the sodium hydroxide solution that mass percentage is 10% and stop step (2) reaction, stir 15 minutes after adjusting pH=7, stratification; Then gained organic phase is poured in saturated nacl aqueous solution, stirs after half an hour stratification again; By gained organic phase evaporate to dryness under vacuum, obtain Avrmectin B
2amonose crystal 48.3g, content 90.9%.
Adopt high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization to gained methylaminoabamectin B2a monose product, HPLC quantitative analysis is as shown in Fig. 1 and table 1; As shown in Figure 2, by above-mentioned characterization, the present embodiment obtains the methylaminoabamectin B2a monose that content is 91.8% to nmr spectrum.
Embodiment 2
Synthesize the methylaminoabamectin B1a monose as above shown in formula I, wherein, X-Y is-CH=CH-, and preparation method is as follows:
(1) take the Avermectin B1a monose that 40g content is 91.4%, add 240g methylene dichloride, dissolve, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 ~-15 DEG C, successively drips 4.0g allyl chlorocarbonate and 6.7g Tetramethyl Ethylene Diamine successively, drip rear continuation stirring reaction 15 minutes;
(3) in the rear gained material of step (2) reaction, add 8g Tetramethyl Ethylene Diamine, 6g dimethyl sulfoxide (DMSO), 13.5g solid phosgene successively, drip rear continuation stirring reaction 15 minutes;
(4) to the phosphoric acid solution termination reaction of 200g2% in the rear gained material of step (3) reaction, stratification after stirring, then separating obtained organic phase 200g saturated sodium bicarbonate aqueous solution is extracted again, stratification, will be separated rear gained organic phase again in 55 DEG C of underpressure distillation, drying 2 hours;
(5) step (4) dry products obtained therefrom is joined 160g1, dissolve in 2-ethylene dichloride, the water-bath being placed in 50 DEG C heats, after temperature rises to 50 DEG C, add 20g heptamethyldisilazane and 20g catalyzer trifluoroacetic acid zinc successively, react 4 hours;
(6) gained material after step (5) reaction is cooled to-10 DEG C, then, add 40g methyl alcohol, more slowly add 2g sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, continues reaction 15 minutes;
(7) in the rear gained material of step (6) reaction, add 0.07g catalyzer tetrakis triphenylphosphine palladium, more slowly add 1.35g sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reacts 2 hours; Then, by 12% acetic acid termination reaction, regulate pH to 6, then pH to 7.5 is regulated with 20% ammoniacal liquor, stratification, then extracts separating obtained organic phase water isopyknic with it once, stratification, in 55 DEG C of underpressure distillation, drying 2 hours, obtain the finished product methylaminoabamectin B1a monose that 28.8g content is 90.1%.
In the above-described embodiments, Avermectin B1a monose used is as shown in formula II, and wherein, Z-W is-CH=CH-, and preparation method is as follows:
(1) 50g Avrmectin B is claimed
1afine powder, adds 300g tetrahydrofuran solvent, stirs and makes it dissolve, and uses subcooling recycle pump that the temperature of solution is down to-10 DEG C ~ 0 DEG C simultaneously;
(2) in step (1) gained abamectin solution, the massfraction of slowly dropping 0 DEG C ~ 10 DEG C is the 200g sulphuric acid soln of 10%, the whole dropping process time used is no less than half an hour, after dropping terminates, continue-10 DEG C ~ 0 DEG C reaction 2 hours, then reaction system is warming up to 35 DEG C, continues reaction 48 hours;
(3) treat that step (2) reaction terminates, be added drop-wise in reaction solution with the sodium hydroxide solution that massfraction is 10% and stop step (2) reaction, stir 15 minutes after adjusting pH=7, stratification; Then gained organic phase is poured in saturated nacl aqueous solution, stirs after half an hour stratification again; By gained organic phase evaporate to dryness under vacuum, obtain Avrmectin B
1amonose crystal 45.2g.
Adopt high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization to gained methylaminoabamectin B1a monose product, HPLC quantitative analysis is as shown in Fig. 3 and table 1; By above-mentioned characterization, the present embodiment obtains the methylaminoabamectin B1a monose that content is 90.1%.
Embodiment 3
Synthesize the methylaminoabamectin B1a monose as above shown in formula I, wherein, X-Y is-CH=CH-, and preparation method is as follows:
(1) take the Avermectin B1a monose that 40g content is 93.0%, add 240g methylene dichloride, dissolve, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 ~-15 DEG C, successively drips 5.0g allyl chlorocarbonate and 8.5g Tetramethyl Ethylene Diamine successively, drip rear continuation stirring reaction 15 minutes;
(3) in the rear gained material of step (2) reaction, add 9.0g Tetramethyl Ethylene Diamine, 7.0g dimethyl sulfoxide (DMSO), 15g solid phosgene successively, drip rear continuation stirring reaction 15 minutes;
(4) to the phosphoric acid solution termination reaction of 200g2% in the rear gained material of step (3) reaction, stratification after stirring, then separating obtained organic phase 200g saturated sodium bicarbonate aqueous solution is extracted again, stratification, will be separated rear gained organic phase again in 55 DEG C of underpressure distillation, drying 2 hours;
(5) step (4) dry products obtained therefrom is joined 180g1, dissolve in 2-ethylene dichloride, the water-bath being placed in 50 DEG C heats, after temperature rises to 50 DEG C, add 20g heptamethyldisilazane and 20g catalyzer trifluoroacetic acid zinc successively, react 4 hours;
(6) gained material after step (5) reaction is cooled to-10 DEG C, then, add 40g methyl alcohol, more slowly add 2.3g sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, continues reaction 15 minutes;
(7) in the rear gained material of step (6) reaction, add 0.06g catalyzer tetrakis triphenylphosphine palladium, more slowly add 1.33g sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reacts 2 hours; Then, by 12% acetic acid termination reaction, regulate pH to 6, then pH to 7.5 is regulated with 20% ammoniacal liquor, stratification, then extracts separating obtained organic phase water isopyknic with it once, stratification, in 55 DEG C of underpressure distillation, drying 2 hours, obtain the finished product methylaminoabamectin B1a monose that 29.2g content is 91.1%.
In the above-described embodiments, Avermectin B1a monose used is as shown in formula II, and wherein Z-W is-CH=CH-, and preparation method is as follows:
(1) 50g Avrmectin B is claimed
1afine powder, adds 400g tetrahydrofuran solvent, stirs and makes it dissolve, and uses subcooling recycle pump that the temperature of solution is down to-5 DEG C ~ 0 DEG C simultaneously;
(2) in step (1) gained abamectin solution, the massfraction of slowly dropping 0 DEG C ~ 5 DEG C is the 200g sulphuric acid soln of 20%, the 50 minutes time used of whole dropping process, after dropping terminates, continue-5 DEG C ~ 0 DEG C reaction 2.5 hours, then reaction system is warming up to 35 DEG C, continues reaction 51.5 hours;
(3) treat that step (2) reaction terminates, be added drop-wise in reaction solution with the sodium hydroxide solution that massfraction is 10% and stop step (2) reaction, stir 15 minutes after adjusting pH=7, stratification; Then gained organic phase is poured in saturated nacl aqueous solution, stirs after half an hour stratification again; By gained organic phase evaporate to dryness under vacuum, obtain Avrmectin B
1amonose crystal 41.3g.
Adopt high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization to gained methylaminoabamectin B1a monose product, wherein, HPLC quantitative analysis is as shown in table 1; By above-mentioned characterization, the present embodiment obtains the methylaminoabamectin B1a monose that content is 91.1%.
Embodiment 4
Synthesize the methylaminoabamectin B1a monose as above shown in formula I, wherein, X-Y is-CH=CH-, and preparation method is as follows:
(1) take the Avermectin B1a monose that 40g content is 92.0%, add 240g methylene dichloride, dissolve, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 ~-15 DEG C, successively drips 5.7g allyl chlorocarbonate and 10g Tetramethyl Ethylene Diamine successively, drip rear continuation stirring reaction 15 minutes;
(3) in the rear gained material of step (2) reaction, add 10g Tetramethyl Ethylene Diamine, 8.0g dimethyl sulfoxide (DMSO), 20g solid phosgene successively, drip rear continuation stirring reaction 15 minutes;
(4) to the phosphoric acid solution termination reaction of 200g2% in the rear gained material of step (3) reaction, stratification after stirring, then separating obtained organic phase 200g saturated sodium bicarbonate aqueous solution is extracted again, stratification, will be separated rear gained organic phase again in 55 DEG C of underpressure distillation, drying 2 hours;
(5) step (4) dry products obtained therefrom is joined 200g1, dissolve in 2-ethylene dichloride, the water-bath being placed in 50 DEG C heats, after temperature rises to 50 DEG C, add 20g heptamethyldisilazane and 20g catalyzer trifluoroacetic acid zinc successively, react 4 hours;
(6) gained material after step (5) reaction is cooled to-10 DEG C, then, add 40g methyl alcohol, more slowly add 2.67g sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, continues reaction 15 minutes;
(7) in the rear gained material of step (6) reaction, add 0.067g catalyzer tetrakis triphenylphosphine palladium, more slowly add 1.33g sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reacts 2 hours; Then, by 12% acetic acid termination reaction, regulate pH to 6, then pH to 7.5 is regulated with 20% ammoniacal liquor, stratification, then extracts separating obtained organic phase water isopyknic with it once, stratification, in 55 DEG C of underpressure distillation, drying 2 hours, obtain the finished product methylaminoabamectin B1a monose that 29.3g content is 91.3%.
In the above-described embodiments, Avermectin B1a monose used is as shown in formula II, and wherein, Z-W is-CH=CH-, and preparation method is with embodiment 3.
Adopt high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization to gained methylaminoabamectin B1a monose product, wherein, HPLC quantitative analysis is as shown in table 1; By above-mentioned characterization, the present embodiment obtains the methylaminoabamectin B1a monose that content is 91.3%.
Embodiment 5
Synthesize the methylaminoabamectin B2a monose as above shown in formula I, wherein, X-Y is-CH
2cH (OH)-, preparation method is as follows:
(1) take 40g avermectin B2a monose, add 200g methylene dichloride, dissolve, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 ~-15 DEG C, successively drips 5.0g allyl chlorocarbonate and 8.5g Tetramethyl Ethylene Diamine successively, drip rear continuation stirring reaction 15 minutes;
(3) in the rear gained material of step (2) reaction, add 9g Tetramethyl Ethylene Diamine, 7g dimethyl sulfoxide (DMSO), 18g solid phosgene successively, drip rear continuation stirring reaction 15 minutes;
(4) to the phosphoric acid solution termination reaction of 200g2% in the rear gained material of step (3) reaction, stratification after stirring, then separating obtained organic phase 200g saturated sodium bicarbonate aqueous solution is extracted again, stratification, will be separated rear gained organic phase again in 55 DEG C of underpressure distillation, drying 2 hours;
(5) step (4) dry products obtained therefrom is joined 180g1, dissolve in 2-ethylene dichloride, the water-bath being placed in 50 DEG C heats, after temperature rises to 50 DEG C, add 20g heptamethyldisilazane and 20g catalyzer trifluoroacetic acid zinc successively, react 4 hours;
(6) gained material after step (5) reaction is cooled to-10 DEG C, then, add 40g methyl alcohol, more slowly add 2.3g sodium borohydride with 0.5g/min, temperature of reaction controls at-10 ~ 0 DEG C, continues reaction 15 minutes;
(7) in the rear gained material of step (6) reaction, add 0.067g catalyzer tetrakis triphenylphosphine palladium, more slowly add 1.33g sodium borohydride with 0.3g/min, temperature of reaction controls at-10 ~ 0 DEG C, reacts 2 hours; Then, by 12% acetic acid termination reaction, regulate pH to 6, then pH to 7.5 is regulated with 20% ammoniacal liquor, stratification, then extracts separating obtained organic phase water isopyknic with it once, stratification, in 55 DEG C of underpressure distillation, drying 2 hours, obtain the finished product methylaminoabamectin B2a monose that 30.4g content is 92.2%.
In the above-described embodiments, avermectin B2a monose used is as shown in formula II, and wherein, Z-W is-CH
2cH (OH)-, preparation method is with embodiment 1.
Adopt high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization to gained methylaminoabamectin B2a monose product, wherein, HPLC quantitative analysis is as shown in table 1; By above-mentioned characterization, the present embodiment obtains the methylaminoabamectin B2a monose that content is 92.2%.
Embodiment 6
Synthesize the methylaminoabamectin B2a monose as above shown in formula I, wherein, X-Y is-CH
2cH (OH)-, preparation method is as follows:
(1) take 40g avermectin B2a monose, add 240g methylene dichloride, dissolve, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 ~-15 DEG C, successively drips 5.7g allyl chlorocarbonate and 10g Tetramethyl Ethylene Diamine successively, drip rear continuation stirring reaction 15 minutes;
(3) in the rear gained material of step (2) reaction, add 10g Tetramethyl Ethylene Diamine, 8g dimethyl sulfoxide (DMSO), 20g solid phosgene successively, drip rear continuation stirring reaction 15 minutes;
(4) to the phosphoric acid solution termination reaction of 200g2% in the rear gained material of step (3) reaction, stratification after stirring, then separating obtained organic phase 200g saturated sodium bicarbonate aqueous solution is extracted again, stratification, will be separated rear gained organic phase again in 55 DEG C of underpressure distillation, drying 2 hours;
(5) step (4) dry products obtained therefrom is joined 200g1, dissolve in 2-ethylene dichloride, the water-bath being placed in 50 DEG C heats, after temperature rises to 50 DEG C, add 20g heptamethyldisilazane and 20g catalyzer trifluoroacetic acid zinc successively, react 4 hours;
(6) gained material after step (5) reaction is cooled to-10 DEG C, then, add 40g methyl alcohol, more slowly add 2.67g sodium borohydride with 0.5g/min, temperature of reaction controls at-6 ~ 0 DEG C, continues reaction 15 minutes;
(7) in the rear gained material of step (6) reaction, add 0.067g catalyzer tetrakis triphenylphosphine palladium, more slowly add 1.33g sodium borohydride with 0.3g/min, temperature of reaction controls at-6 ~ 0 DEG C, reacts 2 hours; Then, by 12% acetic acid termination reaction, regulate pH to 6, then pH to 7.5 is regulated with 20% ammoniacal liquor, stratification, then extracts separating obtained organic phase water isopyknic with it once, stratification, in 55 DEG C of underpressure distillation, drying 2 hours, obtain the finished product methylaminoabamectin B2a monose that 30.2g content is 92.0%.
In the above-described embodiments, avermectin B2a monose used is as shown in formula II, and wherein, Z-W is-CH
2cH (OH)-, preparation method is with embodiment 1.
Adopt high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR) to carry out characterization to gained methylaminoabamectin B2a monose product, wherein, HPLC quantitative analysis is as shown in table 1; By above-mentioned characterization, the present embodiment obtains the methylaminoabamectin B2a monose that content is 92.0%.
Table 1
Application Example
Be described below in conjunction with embody rule example, but the present invention is not limited thereto.
Application examples 1
Methylaminoabamectin monosaccharide compounds sampling obtained for the various embodiments described above is used as sterilant test respectively, and contrasts with existing Avrmectin series products, all samples dilutes 2000 times of uses after all preparing 1.8% missible oil; Initial insect is cotton aphid, and sum is 100.Mortality of insect (%) experimental result is in table 2:
Table 2
Application examples 2
Methylaminoabamectin monosaccharide compounds sampling obtained for the various embodiments described above is used as sterilant test respectively, and contrasts with existing Avrmectin series products, all samples dilutes 2000 times of uses after all preparing 1.8% missible oil; Initial insect is red spider, and sum is 100.Mortality of insect (%) experimental result is in table 3:
Table 3
Show through applied analysis, methylaminoabamectin monosaccharide compounds prepared by the present invention is used as activeconstituents or the auxiliary agent of sterilant, compared with common Avrmectin product, insecticidal activity significantly improves, and insecticidal spectrum is wide, long-lasting is good, noresidue, nuisanceless, especially effective especially to cotton aphid, solve the resistance problems that this class pest produces existing sterilant, destroy lethality drug effect remarkable.
The invention is not restricted to above-mentioned embodiment, those skilled in the art make to any apparent improvement of above-mentioned embodiment or change, all can not exceed the protection domain of design of the present invention and claims.
Claims (10)
1. methylaminoabamectin monosaccharide compounds, has structural formula shown in following formula I:
Formula I
In formula, X-Y is-CH=CH-or-CH
2cH (OH)-.
2. prepare a method for methylaminoabamectin monosaccharide compounds as claimed in claim 1, it is characterized in that, comprise the steps:
(1) in the reactor, with organic solvent, avermectin monosaccharide is dissolved, obtain avermectin monosaccharide solution;
(2) step (1) gained solution is cooled to-30 DEG C ~-15 DEG C, successively drips protective material and acid binding agent successively, continue stirring reaction more than 15 minutes;
(3) in step (2) gained material, add acid binding agent, oxygenant successively, continue stirring reaction more than 15 minutes;
(4) to acid adding termination reaction in step (3) gained material, then, stratification; Then gained organic phase sodium bicarbonate aqueous solution is extracted again, then secondary clearing; Then, the organic phase underpressure distillation that layering is obtained, dry;
(5) by dry for step (4) products obtained therefrom organic solvent dissolution, after being warming up to 50 DEG C ~ 60 DEG C, add heptamethyldisilazane and catalyzer successively, react more than 4 hours;
(6) step (5) gained material is cooled to-10 DEG C to-15 DEG C, then, adds methyl alcohol, then add sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reaction more than 15min;
(7) in step (6) gained material, add catalyzer, then add sodium borohydride, temperature of reaction controls at-10 ~ 0 DEG C, reacts more than 2 hours; Then, in reaction solution, acid adding stops, and adjusts pH=6 ~ 6.5, then, adds adjusting PH with base=7 ~ 7.5, extracted by the isopyknic water of gained organic phase after stratification, then, by organic phase precipitation/drying, obtain methylaminoabamectin monosaccharide compounds.
3. the method preparing methylaminoabamectin monosaccharide compounds according to claim 2, is characterized in that, in described step (3), after adding oxygenant, also adds pro-oxidant; Described pro-oxidant is solid phosgene, and the mass ratio of avermectin monosaccharide and promotor is 2:1 to 3:1.
4. the method preparing methylaminoabamectin monosaccharide compounds according to claim 2, is characterized in that, described avermectin monosaccharide is Avrmectin B
1amonose or Avrmectin B
2amonose.
5. the method preparing methylaminoabamectin monosaccharide compounds according to claim 2, is characterized in that, the temperature of reaction of described step (2) controls at-18 DEG C to-22 DEG C; The temperature of reaction of described step (3) controls at-17 DEG C to-23 DEG C.
6. the method preparing methylaminoabamectin monosaccharide compounds according to any one of claim 2 to 5, it is characterized in that, in described step (1), described organic solvent is methylene dichloride, and the mass ratio of avermectin monosaccharide and methylene dichloride is 1:6 to 1:4;
In described step (2), described protective material is allyl chlorocarbonate, described acid binding agent is Tetramethyl Ethylene Diamine, and the mass ratio of avermectin monosaccharide and allyl chlorocarbonate is 7:1 to 10:1, and the mass ratio of avermectin monosaccharide and Tetramethyl Ethylene Diamine is 4:1 to 6:1;
In described step (3), described acid binding agent is Tetramethyl Ethylene Diamine, and described oxygenant is dimethyl sulfoxide (DMSO); The mass ratio 4:1 to 5:1 of avermectin monosaccharide and Tetramethyl Ethylene Diamine, the mass ratio of avermectin monosaccharide and dimethyl sulfoxide (DMSO) is 5:1 to 7:1;
In described step (4), for termination reaction is phosphoric acid solution to institute's acid adding in step (3) gained material, the mass ratio of phosphoric acid solution used and methylene dichloride is 1:1, and the mass ratio of sodium bicarbonate aqueous solution and methylene dichloride is 1:1;
In described step (5), described organic solvent is ethylene dichloride, described catalyzer is trifluoroacetic acid zinc, the mass ratio of avermectin monosaccharide and ethylene dichloride is 1:5 to 1:4, the mass ratio of avermectin monosaccharide and heptamethyldisilazane is 2:1, and the mass ratio of avermectin monosaccharide and trifluoroacetic acid zinc is 2:1;
In described step (6), the mass ratio of avermectin monosaccharide and methyl alcohol is 1:1, and the mass ratio of avermectin monosaccharide and sodium borohydride is 15:1 to 20:1;
In described step (7), termination reaction acid used is acetic acid, adjusts pH alkali used to be ammoniacal liquor; Described catalyzer is tetrakis triphenylphosphine palladium, and the mass ratio of avermectin monosaccharide and tetrakis triphenylphosphine palladium is 600:1, and the mass ratio of avermectin monosaccharide and sodium borohydride is 30:1.
7. the method preparing methylaminoabamectin monosaccharide compounds according to claim 6, is characterized in that, in described step (1) and (5), organic solvent used is 1,2-ethylene dichloride.
8. the method preparing methylaminoabamectin monosaccharide compounds according to claim 6, it is characterized in that, in described step (4), the mass percent concentration of termination reaction phosphoric acid solution used is 2%, and described sodium bicarbonate aqueous solution is saturated solution; In described step (7), the mass percent concentration of acetic acid added by termination reaction is 12%, and adjust pH alkali used to be ammoniacal liquor, the mass percent concentration of ammoniacal liquor is 20%.
9. the method preparing methylaminoabamectin monosaccharide compounds according to claim 6, is characterized in that: in step (6) and (7), when adding sodium borohydride, and control feed rate is 0.3g/min ~ 0.5g/min.
10. a purposes for methylaminoabamectin monosaccharide compounds as claimed in claim 1, is characterized in that: described avermectin monosaccharide compound is as the activeconstituents of agricultural chemicals or auxiliary agent.
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| CN107337682A (en) * | 2016-11-22 | 2017-11-10 | 石家庄市兴柏生物工程有限公司 | 13 are acylated avermectin B2a aglycone derivative and its production and use |
| CN108902163A (en) * | 2018-08-08 | 2018-11-30 | 河北威远生物化工有限公司 | A kind of emamectin benzoate B2 benzoate osmotic pump tablet and preparation method thereof |
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| CN108902163A (en) * | 2018-08-08 | 2018-11-30 | 河北威远生物化工有限公司 | A kind of emamectin benzoate B2 benzoate osmotic pump tablet and preparation method thereof |
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