CN104402953B - Avermectin monosaccharide compound and its production and use - Google Patents
Avermectin monosaccharide compound and its production and use Download PDFInfo
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- CN104402953B CN104402953B CN201410706420.1A CN201410706420A CN104402953B CN 104402953 B CN104402953 B CN 104402953B CN 201410706420 A CN201410706420 A CN 201410706420A CN 104402953 B CN104402953 B CN 104402953B
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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
- C07H17/08—Hetero rings containing eight or more ring members, e.g. erythromycins
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- 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 present invention relates to desinsection technical field of pesticide, more particularly to avermectin monosaccharide compound and its production and use, it is sloughed an olive glycosyl by carrying out chemical modification on the basis of AVM and obtain avermectin monosaccharide compound.Compared with prior art, avermectin monosaccharide compound of the present invention is used as insecticide compared with common AVM product, with drug effect height, wide insecticidal spectrum, lasting period length, noresidue and nuisanceless feature, but also has the advantages that instant effect and non-resistant；Larva and mite class common insect pests activity especially to lepidopterous insects is high, and existing stomach poison function has action of contace poison concurrently again, just has very reliable and stable prevention effect under low-down dosage；In addition, while being significantly improved compared to common AVM product insecticidal activity, its insecticidal range is almost throughout all adult and ovum with agriculture relevant nematode and arthropod, and destruction lethal drug effect is notable, suitable in association area popularization and application.
Description
Technical field
The present invention relates to desinsection technical field of pesticide, more particularly to avermectin monosaccharide compound and preparation method thereof and
Purposes.
Background technology
AVM (Avermectin, abbreviation AVM) is that a class has mite killing, ten hexa-atomic macrolide chemical combination of desinsection
Thing, is the Avid kyowamycin fermentation life in streptomycete, occupies more important status in agricultural chemicals prevention insect system, it has low
Poison, efficiently, high selection, environmental protection and the characteristic in biological source desinsection, substantially overcome the difficult settled high poison of traditional agricultural chemicals,
Resistance and the problems such as to environmental effects.AVM has turned at present one of maximally efficient insecticide in the world.But,
With the popularization and popularization of AVM and its downstream product in recent years, its drug-fast increase, along with itself has heat drop
Solution and photodegradative feature, the lasting period shorten, compared to other agricultural chemicals advantage start it is less and less.Accordingly, it would be desirable to AVM hereinafter
Rhzomorph is improved, and is used for the prevention effect in pest control region to improve it.
The content of the invention
The purpose of the present invention is, the problem of existing for prior art there is provided a kind of avermectin monosaccharide compound and its
Preparation method and purposes.
The technical scheme of the present invention that solves the problems, such as is：A kind of avermectin monosaccharide compound, with knot such as following formula (I) Suo Shi
Structure formula：
Formula (I)
In formula, X-Y is-CH=CH- or-CH2-CHOH-。
The preparation method of above-mentioned avermectin monosaccharide compound, comprises the following steps：
(1) in the reactor, AVM is dissolved with organic solvent, obtains abamectin solution；
(2) into abamectin solution obtained by step (1), acid adding is catalyzed desugar, keeps reaction 50 hours~58 hours；
(3) terminate after step (2) reaction, adjust after PH=7, stratification；Then gained organic phase is cleaned, then secondary clearing
Afterwards, isolated organic phase is evaporated, obtains avermectin monosaccharide.
Further, it is described in step (1) in the preparation method of above-mentioned avermectin monosaccharide compound of the invention
Organic solvent requirement will also ensure the solubility to AVM for that should be dissolved each other with water with arbitrary proportion after miscible with water, excellent
Elect tetrahydrofuran as；In step (2), institute's acid adding be sulfuric acid, plus sulfuric acid carry out catalysis desugar, can ensure catalysis desugar effect
The lactone macrocyclic structure of AVM is avoided damage to while fruit.
Preferably,, will in the step (1) in the preparation method of above-mentioned avermectin monosaccharide compound of the invention
In AVM addition tetrahydrofuran after stirring and dissolving, gained abamectin solution is cooled to -10 DEG C~0 DEG C；In the step
Suddenly in (2), the temperature of the sulfuric acid solution is 0 DEG C~10 DEG C.
Preferably, in the preparation method of above-mentioned avermectin monosaccharide compound of the invention, in the step (2), to
The time control of sulfuric acid solution is added dropwise in abamectin solution obtained by step (1) at 30 minutes~50 minutes；Sulfuric acid be added dropwise is molten
The weight/mass percentage composition of liquid is 10%~30%, is added dropwise into abamectin solution obtained by step (1) after sulfuric acid solution, keep-
10 DEG C~0 DEG C is reacted 2 hours~2.5 hours, and reaction temperature then is risen into 33 DEG C~37 DEG C, continues reaction 48 hours~54 small
When.
Preferably, in the preparation method of above-mentioned avermectin monosaccharide compound of the invention, in the step (1), institute
Organic solvent is stated for tetrahydrofuran, the mass ratio of AVM and tetrahydrofuran is 1:6~1:10.
Preferably, in the preparation method of above-mentioned avermectin monosaccharide compound of the invention, in the step (2), to
It is added dropwise in abamectin solution obtained by step (1) after sulfuric acid solution, the weight/mass percentage composition of sulfuric acid is in gained mixed reaction solution
2%~6%.
Further, in the preparation method of above-mentioned avermectin monosaccharide compound of the invention, in the step (3),
Terminated with sodium hydroxide solution after step (2) reaction；Cleaned after gained organic phase, then secondary clearing, will separated with sodium chloride solution
Obtained organic phase vacuum drying, obtains avermectin monosaccharide compound；Preferably, in the step (3), step is terminated
(2) weight/mass percentage composition for reacting sodium hydroxide solution used is 10%, and sodium chloride solution used in cleaning organic phase is saturation chlorine
Change sodium solution.
Present invention also offers the purposes of avermectin monosaccharide compound, the avermectin monosaccharide compound is used as agricultural chemicals
Active component or auxiliary agent, it is preferred that active component or auxiliary agent as insecticide, with common AVM product ratio
Compared with insecticidal activity can improve more than 3 times, and drug effect maintains to reach 15 days.
Avermectin monosaccharide compound prepared by the present invention uses high performance liquid chromatograph (HPLC) and nuclear magnetic resonance matter
Analysis of spectrum (NMR) carries out sign identification, and yield reaches more than 90%, and shows with reference to its pesticidal applications effect analysis, the present invention
Make it slough an olive glycosyl to obtain avermectin monosaccharide chemical combination by carrying out chemical modification on the basis of AVM
Thing, compared with common AVM product, with drug effect height, wide insecticidal spectrum, lasting period length, noresidue and nuisanceless feature, and
And also there is instant effect and non-resistant；Larva and mite class common insect pests activity especially to lepidopterous insects is high,
Existing stomach poison function has action of contace poison concurrently again, just has very reliable and stable prevention effect under low-down dosage；This
Outside, while being significantly improved compared to common AVM product insecticidal activity, its insecticidal range almost throughout it is all with it is agriculture
Relevant nematode and the adult of arthropod and ovum, destruction lethal drug effect are notable, suitable in association area popularization and application.
Brief description of the drawings
Fig. 1 is the HPLC quantitative analysis spectrograms of the gained Avermectin B1a monose product of the embodiment of the present invention 1；
Fig. 2 is the nmr spectrum of the gained Avermectin B1a monose product of the embodiment of the present invention 1；
Fig. 3 is the nmr spectrum of the gained avermectin B2a monose product of the embodiment of the present invention 2.
Embodiment
In the present invention there is provided avermectin monosaccharide compound, with the structural formula as shown in following formula (I)：
Formula (I)
In formula, X-Y is-CH=CH- or-CH2-CHOH-。
In the present invention, the preparation method of avermectin monosaccharide compound performs following steps：
(1) in the reactor, AVM is dissolved with organic solvent, obtains abamectin solution；
(2) into abamectin solution obtained by step (1), slow acid adding is catalyzed desugar, keeps reaction 50 hours~58 small
When；
(3) terminate after step (2) reaction, adjust after PH=7, stratification；Then gained organic phase is cleaned, then secondary clearing
Afterwards, isolated organic phase is evaporated, obtains avermectin monosaccharide.
In the preparation method of above-mentioned avermectin monosaccharide compound of the invention, to make reaction system react completely,
In step (1), organic solvent requirement also to ensure for that should be dissolved each other with water with arbitrary proportion after miscible with water to Ah
The solubility of rhzomorph is tieed up, research staff tests by hundreds of solvent, it is considered to which the reaction system reactions change of each step and entirety will
Ask, preferably tetrahydrofuran is as solvent, so as to ensure the smooth generation of follow-up reaction；In step (2), institute's acid adding is sulphur
Acid, plus sulfuric acid carry out catalysis desugar, and the lactone big ring of AVM can be avoided damage to while catalysis desugar effect is ensured
Structure.
In the present invention prepares the method for avermectin monosaccharide compound, effect is fully realized to enable to prepare each stage
Really, in the step (1), the organic solvent is tetrahydrofuran, and AVM is added in tetrahydrofuran after stirring and dissolving,
Gained abamectin solution is cooled to -10 DEG C~0 DEG C with sub-cooled circulating pump；In the step (2), low temperature cold is first used
But the sulfuric acid solution of preparation is cooled to 0 DEG C~10 DEG C by circulating pump, so that ensureing the temperature of itself and abamectin solution tends to one
Cause, and then be beneficial to make reaction uniformly carry out.
It is the product and reaction speed of effective control reaction in the present invention prepares the method for avermectin monosaccharide compound
Degree, in the step (2), into abamectin solution obtained by step (1) sulfuric acid solution being added dropwise need to slowly be carried out, dropwise addition when
Between control, at 30 minutes~50 minutes, to avoid partial carbonization phenomenon；Slowly dripped into abamectin solution obtained by step (1)
Plus after sulfuric acid solution, kept for -10 DEG C~0 DEG C react 2 hours~2.5 hours, reaction temperature is then risen to 33 DEG C~37 DEG C, after
Continuous reaction 48 hours~54 hours.
In the present invention prepares the method for avermectin monosaccharide compound, to make each highly effective reaction step by step obtain target production
Thing, in the step (1), the organic solvent is tetrahydrofuran, and the mass ratio of AVM and tetrahydrofuran is 1:6~1:
10；In the step (2), the weight/mass percentage composition that sulfuric acid solution is added dropwise is 10%~30%, to AVM hereinafter obtained by step (1)
It is added dropwise in rhzomorph solution after sulfuric acid solution, the weight/mass percentage composition of sulfuric acid is 2%~6% in gained mixed reaction solution；Described
In step (3), terminated with sodium hydroxide solution after step (2) reaction；To ensure the high extraction yield of organic phase, saturated sodium-chloride is used
Solution is cleaned to gained organic phase, then after secondary clearing, isolated organic phase is dried in vacuo, AVM list is obtained
Sugar, it is preferable that the weight/mass percentage composition for terminating step (2) reaction sodium hydroxide solution used is 10%, used in cleaning organic phase
Sodium chloride solution is saturated nacl aqueous solution.
AVM ester type compound prepared by the present invention uses high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy
(NMR) sign identification is carried out.
In addition, present invention also offers the purposes of avermectin monosaccharide compound, as agricultural chemicals active component or help
Agent, it is preferable that active component or auxiliary agent as insecticide, through application test, insect just stops taking food after medication 5 minutes,
Desinsection peak is can reach in 48~72 hours, is compared with common AVM product, insecticidal activity can improve more than 3 times, medicine
Effect maintenance can be reached 15 days.
With reference to specific embodiment, the present invention is further illustrated, but protection scope of the present invention is not limited to
This.
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material, reagent used etc., unless otherwise instructed, are commercially obtained in following embodiments.
Embodiment 1
The avermectin monosaccharide compound as shown in above formula (I) is synthesized, wherein, R is-CH=CH-, i.e. AVM B1aIt is single
Sugar, shown in structure such as following formula (II)：
Above-mentioned AVM B1aThe preparation method of monose：
(1) 50g AVMs B is claimed1aFine powder, adds 300g tetrahydrofuran solvents, stirring dissolves it, while using low temperature
The temperature of solution is down to -10 DEG C~0 DEG C by coolant circulation pump；
(2) 200g that the mass fraction that 0 DEG C~10 DEG C are slowly added dropwise into abamectin solution obtained by step (1) is 10%
Sulfuric acid solution, the time used in whole dropwise addition process is no less than half an hour, after completion of dropwise addition, continues small in -10 DEG C~0 DEG C reaction 2
When, reaction system is then warming up to 35 DEG C, continues to react 48 hours；
(3) treat that step (2) reaction terminates, termination in reaction solution is added drop-wise to for 10% sodium hydroxide solution with mass fraction
Step (2) is reacted, and is adjusted and is stirred 15 minutes after pH=7, stratification；Then gained organic phase is poured into saturated nacl aqueous solution
In, stratification again after stirring half an hour；Gained organic phase is evaporated under vacuum, AVM B is produced1aMonose is brilliant
Body 45.2g, content 92.3%.
To gained AVM B1aMonose product is entered using high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR)
Row characterizes identification, and HPLC quantitative analyses are as shown in Fig. 1 and table 1；Nmr spectrum as shown in Fig. 2 identified by above-mentioned sign,
The product as shown in formula (II) is made in the present embodiment, and yield is 90.23%.
Embodiment 2
The avermectin monosaccharide compound as shown in above formula (I) is synthesized, wherein, R is-CH2- CHOH-, i.e. AVM B2a
Monose, shown in structure such as following formula (III)：
Above-mentioned AVM B2aThe preparation method of monose：
(1) 50g AVMs B is claimed2A fine powders, add 400g tetrahydrofuran solvents, stirring dissolves it, while using low
The temperature of solution is down to -10 DEG C~0 DEG C by warm coolant circulation pump；
(2) it is 20% that 0 DEG C~10 DEG C of quality point content is slowly added dropwise into abamectin solution obtained by step (1)
100g sulfuric acid solutions, the time used in whole dropwise addition process is no less than half an hour, after completion of dropwise addition, continues in -10 DEG C~0 DEG C reaction
2 hours, reaction system is then warming up to 35 DEG C, continues to react 48 hours；
(3) treat that step (2) reaction terminates, be added drop-wise to quality point content for 10% sodium hydroxide solution in reaction solution eventually
Rapid (2) reaction is halted, adjusts and is stirred 15 minutes after pH=7, stratification；Then gained organic phase is poured into saturated sodium-chloride molten
In liquid, stratification again after stirring half an hour；Gained organic phase is evaporated under vacuum, AVM B is produced2aMonose
Crystal 47.5g, content 93.9%.
To gained AVM B2aMonose product is entered using high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR)
Row characterizes identification, wherein, as shown in table 1, nmr spectrum is as shown in Figure 3 for HPLC quantitative analyses；Identified by above-mentioned sign,
The product as shown in formula (III) is made in the present embodiment, and yield is 91.06%.
Embodiment 3
One kind AVM B as shown in formula (II)1The preparation method of a monose, comprises the following steps：
(1) 50g AVMs B is claimed1aFine powder, adds 400g tetrahydrofuran solvents, stirring dissolves it, while using low temperature
The temperature of solution is down to -10 DEG C~0 DEG C by coolant circulation pump；
(2) 200g that the mass fraction that 0 DEG C~10 DEG C are slowly added dropwise into abamectin solution obtained by step (1) is 15%
Sulfuric acid solution, the 50 minutes time used in whole dropwise addition process, after completion of dropwise addition, continue -10 DEG C~0 DEG C react 2.5 hours, so
Reaction system is warming up to 35 DEG C afterwards, continues to react 51.5 hours；
(3) treat that step (2) reaction terminates, termination in reaction solution is added drop-wise to for 10% sodium hydroxide solution with mass fraction
Step (2) is reacted, and is adjusted and is stirred 15 minutes after pH=7, stratification；Then gained organic phase is poured into saturated nacl aqueous solution
In, stratification again after stirring half an hour；Gained organic phase is evaporated under vacuum, AVM B is produced1aMonose is brilliant
Body 41.3g, content 89.6%.
To gained AVM B1aMonose product is entered using high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR)
Row characterizes identification, wherein, HPLC quantitative analyses are as shown in table 1；Identified by above-mentioned sign, the present embodiment is made such as formula (II) institute
The product shown, yield is 87.12%.
Embodiment 4
One kind AVM B as shown in formula (III)2The preparation method of a monose, comprises the following steps：
(1) 50g AVMs B is claimed2A fine powders, add 500g tetrahydrofuran solvents, stirring dissolves it, while using low
The temperature of solution is down to -10 DEG C~0 DEG C by warm coolant circulation pump；
(2) it is 30% that 0 DEG C~10 DEG C of weight/mass percentage composition is slowly added dropwise into abamectin solution obtained by step (1)
100g sulfuric acid solutions, the time used in whole dropwise addition process is no less than half an hour, after completion of dropwise addition, continues in -10 DEG C~0 DEG C reaction
2 hours, reaction system is then warming up to 37 DEG C, continues to react 49 hours；
(3) treat that step (2) reaction terminates, be added drop-wise to weight/mass percentage composition for 10% sodium hydroxide solution in reaction solution
Step (2) reaction is terminated, adjusts and is stirred 15 minutes after pH=7, stratification；Then gained organic phase is poured into saturated sodium-chloride
In solution, stratification again after stirring half an hour；Gained organic phase is evaporated under vacuum, AVM B is produced2aIt is single
Sugar crystal 48.3g, content 90.9%.
To gained AVM B2aMonose product is entered using high performance liquid chromatograph (HPLC) and nuclear magnetic resonance spectroscopy (NMR)
Row characterizes identification, wherein, HPLC quantitative analyses are as shown in table 1；Identified by above-mentioned sign, the present embodiment is made such as formula (III) institute
The product shown, yield is 89.67%.
Table 1
Application Example
Illustrated with reference to concrete application example, but the invention is not restricted to this.
Avermectin monosaccharide compound sampling made from the various embodiments described above is tested respectively as insecticide, owned
Sample is prepared 1000 times of dilution after 0.5% missible oil and used；Initial insect populations are 100.Insect death assay result is shown in
Table 2：
Table 2
Show by applied analysis, the avermectin monosaccharide compound prepared by the present invention is used as the active component of insecticide
Or auxiliary agent, compared with common AVM product, with drug effect height, wide insecticidal spectrum, lasting period length, noresidue and nuisanceless spy
Point, but also there is instant effect and non-resistant；Larva and mite class common insect pests activity especially to lepidopterous insects
High, existing stomach poison function has action of contace poison concurrently again, just has very reliable and stable preventing and treating effect under low-down dosage
Really；Moreover, being compared with common AVM product, its insecticidal range is almost throughout all dynamic with agriculture relevant nematode and segmental appendage
The adult of thing and ovum, destruction lethal drug effect are notable；Use evil after the avermectin monosaccharide compound 5 minutes prepared by the present invention
Worm just stops taking food, and desinsection peak can be reached in 48~72 hours, and drug effect is able to maintain that more than 15 days, insecticidal activity energy
Enough improve more than 3 times.
The invention is not restricted to above-mentioned embodiment, made any to above-mentioned embodiment aobvious of those skilled in the art and
The improvement or change being clear to, all without the design beyond the present invention and the protection domain of appended claims.
Claims (5)
1. the method that one kind prepares the avermectin monosaccharide compound as shown in formula (I),
In formula (I), X-Y is-CH=CH- or-CH2-CHOH-；
It is characterised in that it includes following steps：
(1) in the reactor, with tetrahydrofuran by AVM B1a/B2aFine powder dissolves, and obtains AVM B1a/B2aSolution, by institute
Obtain AVM B1a/B2aSolution cools to -10 DEG C~0 DEG C；
(2) to AVM B obtained by step (1)1a/B2aAdd sulfuric acid catalysis desugar in solution, the time control of sulfuric acid is added dropwise 30
Minute~50 minutes, the temperature of the sulfuric acid solution is 0 DEG C~10 DEG C, is kept for -10 DEG C~0 DEG C react 2 hours~2.5 hours,
Then reaction temperature is risen to 33 DEG C~37 DEG C, continues to react 48 hours~54 hours；
(3) terminate after step (2) reaction, adjust after PH=7, stratification；Then gained organic phase is cleaned, then after secondary clearing,
Isolated organic phase is evaporated, AVM B is obtained1a/B2aMonose.
2. the method for avermectin monosaccharide compound of the preparation according to claim 1 as shown in formula (I), its feature exists
In in the step (1), the mass ratio of AVM and tetrahydrofuran is 1:6~1:10.
3. the method for avermectin monosaccharide compound of the preparation according to claim 1 as shown in formula (I), its feature exists
In in the step (2), the weight/mass percentage composition that sulfuric acid solution is added dropwise is 10%~30%, to AVM hereinafter obtained by step (1)
It is added dropwise in rhzomorph solution after sulfuric acid solution, the weight/mass percentage composition of sulfuric acid is 2%~6% in gained mixed reaction solution.
4. the method for avermectin monosaccharide compound of the preparation according to claim 1 as shown in formula (I), its feature exists
In in the step (3), after sodium hydroxide solution termination step (2) reaction；Gained is cleaned with sodium chloride solution organic
After phase, then secondary clearing, isolated organic phase is dried in vacuo, avermectin monosaccharide compound is obtained.
5. the method for avermectin monosaccharide compound of the preparation according to claim 4 as shown in formula (I), its feature exists
In in the step (3), the weight/mass percentage composition for terminating step (2) reaction sodium hydroxide solution used is 10%, and cleaning has
Sodium chloride solution used in machine phase is saturated nacl aqueous solution.
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Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4206205A (en) * | 1977-10-03 | 1980-06-03 | Merck & Co., Inc. | Monosaccharide and aglycone derivatives of C-076 |
| US4203976A (en) * | 1978-08-02 | 1980-05-20 | Merck & Co., Inc. | Sugar derivatives of C-076 compounds |
| US4333925A (en) * | 1981-05-11 | 1982-06-08 | Merck & Co., Inc. | Derivatives of C-076 compounds |
| AU9785698A (en) * | 1997-10-02 | 1999-04-27 | Microcide Pharmaceuticals, Inc. | Fungal efflux pump inhibitors |
| CN1502239A (en) * | 2002-11-26 | 2004-06-09 | 中国科学院生态环境研究中心 | Preparation for novel mite-killing and pesticide compound |
| GB0229804D0 (en) * | 2002-12-20 | 2003-01-29 | Syngenta Participations Ag | Avermection b1 and avermectin b1 monosaccharide derivatives having an alkoxymethyl substituent in the 4"- or 4'-position |
| GB0302309D0 (en) * | 2003-01-31 | 2003-03-05 | Syngenta Participations Ag | Avermectin monosaccharide derivatives substituted in the 4 -position having pesticidal properties |
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