CN105969815A - Biological preparation method of (S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic methyl ester - Google Patents
Biological preparation method of (S)-5-chloro-2,3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic methyl ester Download PDFInfo
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Abstract
The invention discloses a biological preparation method of (S)-5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic methyl ester, 5-chloro-2,3-dihydro-1-oxo-1H-indene-2-carboxylic methyl ester serves as a substrate, the substrate conducts a reduction reaction under existence of a biological catalyst, a cofactor and a cofactor regeneration system to generate the (S)-5-chloro-2, 3-dihydro-2-hydroxy-1-oxo-1H-indene-2-carboxylic methyl ester, the biological catalyst is monooxygenase, the cofactor regeneration system comprises glucose and glucose dehydrogenase, and the reduction reaction is conducted in water-phase buffer liquid with the temperature being 20-30 DEG C and the pH being 7.0-8.0. Compared with the prior art, hazardous articles and organic hydroxylation reagents are not used in the whole reaction process, economy of the whole production process is greatly improved, environmental friendliness is achieved, and the substrate conversion rate is high.
Description
Technical field
The present invention relates to technical field of biochemical industry, be specifically related to one (S)-5-chloro-2,3-dihydro-2-hydroxyl
The biological preparation method of-1-oxo-1H-indenes-2-carboxylate methyl ester.
Background technology
Add up according to the World Food Programme, owing to the loss caused to crops of invading and harassing of disease pest and weed is equivalent to generation
/ 3rd of the annual crop yield in boundary.China's Pesticidal products is with organophosphor, the contour poison of carbamate at present
Pesticide is main, and exploitation is efficient, low toxicity, environmentally safe green pesticide are extremely urgent.
Diazines insecticide be it is found that after pyrethrin, imidacloprid and other pesticide have draw time
Novel pesticide for meaning.Indoxacarb (indoxacarb) is novel the two of du pont company's exploitation
Piperazine class (oxadiazine) insecticide, trade name Ammate/Avatar, suppresses broad spectrum disinfestation for sodium channel
Agent, is respectively provided with, to almost all of lepidoptera pest, the ability of killing, and has insecticidal activity height, Environmental compatibility
Good, low to mammalian toxicity, to birds, Fish and the advantage of beneficial insect safety, it is that the high poison of replacement is organic
The preferable kind of phosphorus pesticide.
Indoxacarb (indoxacarb)
The preparation method of indoxacarb it is crucial that obtain its chiral intermediate (S)-5-chloro-2,3-dihydro-2-hydroxyl
-1-oxo-1H-indenes-2-carboxylate methyl ester (1).From the point of view of green chemistry angle, from its precursor 5-chloro-2,3-
Dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester one step hydroxylation (2) is most efficient method:
The route of presently disclosed production compound 1 has patent disclosed in du pont company (DUPONT), as
WO 1992011249, US 5462938, US 5510505 and WO 199529171 etc., this route uses former
Material hydrogen, needs autoclave to react, there is the potential safety hazards such as blast；And on the basis of above patent
Make some route improved, such as CN 105152958, CN 104193696 and CN 104193620 etc..
Above-mentioned chemical route, is carried out the most in organic solvent, is required to add organic hydroxylation reagent (such as organic hydrazine
And quinine), such actual limited source, expensive, therefore its economy and environment friendly have
Wait to improve.
Summary of the invention
It is an object of the invention to provide one (S)-5-chloro-2,3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylic
The biological preparation method of acid methyl ester, which overcomes the deficiencies in the prior art, and good economy performance is environmentally friendly.
For reaching above-mentioned purpose, the technical solution used in the present invention is: a kind of (S)-5-chloro-2,3-dihydro-2-
The biological preparation method of hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester, it is with 5-chloro-2,3-dihydro-1-oxo
-1H-indenes-2-carboxylate methyl ester is substrate, and this substrate is at biocatalyzer, cofactor and cofactor regeneration system
In the presence of, occur reduction reaction to generate (S)-5-chloro-2,3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylic
Acid methyl ester, described biocatalyzer is monooxygenase, described cofactor regeneration system include glucose and
Glucose dehydrogenase, described reduction reaction temperature be 20-30 DEG C, pH be the aqueous phase buffering of 7.0-8.0
Liquid is carried out, in initial action system, described substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylic
The concentration of acid methyl ester is 15-25mg/mL, described monooxygenase and substrate 5-chloro-2,3-dihydro-1-oxo-
The mass ratio of 1H-indenes-2-carboxylate methyl ester is 1:1-20.Preferably, described substrate 5-chloro-2,3-dihydro-1-
The concentration of oxo-1H-indenes-2-carboxylate methyl ester is 20mg/mL, described monooxygenase and substrate 5-chloro-2,3-
The mass ratio of dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester is 1:10.
Preferably, described monooxygenase is that the trade mark produced purchased from Suzhou Chinese biotechnology of enzymes company limited is
The combination of one or more in the monooxygenase of EW1531, EW1535, EW1536 or EW1538.
It is further preferred that described monooxygenase is to produce purchased from Suzhou Chinese biotechnology of enzymes company limited
The trade mark is the monooxygenase of EW1535.
Preferably, in initial action system, described glucose: glucose dehydrogenase: 5-chloro-2,3-bis-
The mass ratio of hydrogen-1-oxo-1H-indenes-2-carboxylate methyl ester is 1.6-15:1:1-20；It is more highly preferred to, described
Glucose: feeding intake of glucose dehydrogenase: 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester
Mass ratio is 15:1:10.
Preferably, described cofactor is NADP, itself and 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylic
The mass ratio of acid methyl ester is 1:1-100, it is further preferable that NADP Yu 5-chloro-2,3-dihydro-1-oxo-1H-
The mass ratio of indenes-2-carboxylate methyl ester is 1:100.
Preferably, described reaction is carried out under the conditions of cosolvent.
It is further preferred that described cosolvent be hexamethylene, PEG400, polyethylene glycol 200,
The combination of one or more in glycerol, toluene, ethylene glycol, Tween-60.
Preferably, described aqueous phase buffer solution is phosphate buffered solution.
Preferably, specific implementation process is as follows: be sequentially added into described aqueous phase buffering in reaction vessel molten
Liquid, substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester, after stirring, add institute
The monooxygenase stated, cofactor, glucose, glucose dehydrogenase, shake under 20-30 DEG C of temperature conditions
Reaction, HPLC detects reaction process, when conversion ratio reaches 90-99%, filters after dezymotizing, adds equal-volume
Ethyl acetate repeatedly extracts, and merges organic facies, obtains (S)-5-chloro-2,3-dihydro-2-after sloughing solvent
Hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester product.
Due to the utilization of technique scheme, the present invention compared with prior art has the advantage that the present invention
Have employed enzyme by chloro-for chloro-for 5-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester reduction generation (S)-5-
2,3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl esters, whole preparation process is carried out in aqueous phase,
Compared with prior art, it is not necessary to use hydrogen, do not have the hidden danger of blast；Simultaneously without adding organic hydroxyl
Change reagent, good economy performance, the most environmentally friendly, and the conversion ratio of substrate is high, product ee value is high.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be further described in detail, but the present invention be not limited to
Lower embodiment.The implementation condition used in embodiment can do further tune according to specifically used different requirement
Whole, not marked implementation condition is the condition in normal experiment.
Embodiment 1
In 2mL centrifuge tube, the phosphate-buffered being sequentially added into 975 μ L 100mM pH 8.0 is molten
Liquid, adds substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester 2mg, methanol 25 μ L,
After stirring, add different monooxygenase (from Suzhou Chinese biotechnology of enzymes company limited) 2mg,
NADP 2mg, glucose 3.2mg, glucose dehydrogenase 2mg, concussion reaction at 30 DEG C, 24 hours
HPLC detects reaction result such as table 1.
Table 1
| EW1531 | EW1535 | EW1536 | EW1538 | |
| Conversion ratio | 33% | 48.3% | 47.3% | 43.9% |
| Product ee | 96.1% | 96.7% | 92.5% | 100% |
As can be seen from Table 1, in the case of other reaction conditions are identical, using the trade mark is EW1535's
Monooxygenase, the conversion ratio of substrate is the highest, and the monooxygenase using the trade mark to be EW1538, product e e-value
The highest.
Embodiment 2
In 5mL centrifuge tube, the phosphate-buffered being sequentially added into 1950 μ L 100mM pH 8.0 is molten
Liquid, adds substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester 4mg, methanol 50 μ L,
After stirring, add monooxygenase EW 1538 (from Suzhou Chinese biotechnology of enzymes company limited) 1mg,
NADP 0.5mg, glucose 6mg, glucose dehydrogenase 1mg, concussion reaction, HPLC under different temperatures
Detection reaction result such as table 2.
Table 2
| Temperature/DEG C | 20 | 30 | 40 |
| 1h | 27.9% | 24.5% | 7.0% |
| 3h | 57.5% | 67.6% | 7.5% |
| 24h | 67.6% | 71.4% | 7.6% |
As can be seen from Table 2, in the case of other reaction conditions are identical, react under 30 DEG C of temperature conditionss
Time, the conversion ratio of substrate is the highest.
Embodiment 3
In 5mL centrifuge tube, it is sequentially added into the buffer solution of 1950 μ L 100mM differences pH, adds
Substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester 4mg, methanol 50 μ L, stir
After, add monooxygenase EW1538 (from Suzhou Chinese biotechnology of enzymes company limited) 1mg, NADP 0.5
Mg, glucose 6mg, glucose dehydrogenase 1mg, concussion reaction at 30 DEG C, HPLC detects reaction result
Such as table 3.
Table 3
| pH | 5.5 | 6.0 | 7.0 | 8.0 |
| 1h | 14.9% | 20.7% | 27.0% | 24.5% |
| 3h | 23.9% | 39.8% | 72.8% | 67.6% |
| 24h | 19.4% | 33.6% | 80.1% | 71.4% |
As can be seen from Table 3, in the case of other reaction conditions are identical, delay at the aqueous phase that pH is 7.0
Carrying out above-mentioned reaction in dissolved liquid, the conversion ratio of substrate is the highest.
Embodiment 4
In 5mL centrifuge tube, it is sequentially added into the buffer solution of 1900 μ L 100mM pH 7.0, adds
Substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester 4mg, different cosolvent 100 μ L,
After stirring, add monooxygenase EW 1538 (from Suzhou Chinese biotechnology of enzymes company limited) 1mg,
NADP 0.5mg, glucose 6mg, glucose dehydrogenase 1mg, concussion reaction under 30 degrees Celsius, 24
Hour HPLC detects reaction result such as table 4.
Table 4
| Cosolvent | Matched group | Hexamethylene | PEG400 | PEG200 | Glycerol | Toluene | Ethylene glycol |
| 2h | 10.4% | 17.58% | 17.21% | 14.63% | 14.10% | 10.50% | 10.7% |
| 4h | 15.3% | 25.55% | 22.06% | 20.21% | 20.57% | 19.07% | 16.5% |
| Cosolvent | Polysorbate60 | TritonX | DMSO | Methanol | Hexanol | MTBE | |
| 2h | 7.6% | 10.5% | 9.9% | 8.3% | 7.5% | 6.9% | |
| 4h | 16.9% | 15.8% | 14.1% | 14.1% | 12.6% | 12.1% |
As can be seen from Table 4, in the case of other reaction conditions are identical, with cyclohexane give as cosolvent
Time, the conversion ratio of substrate is the highest.
Embodiment 5
In 100mL reaction vessel, it is sequentially added into the phosphate-buffered of 47.5mL 100mM pH 7.0
Solution, adds substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester 1g, hexamethylene 2.5
ML, after stirring, adds monooxygenase EW 1538 (from Suzhou Chinese biotechnology of enzymes company limited) 0.1
G, NADP 0.01g, glucose 1.5g, glucose dehydrogenase 0.1g, concussion reaction at 30 DEG C, 24
Hour HPLC detection reaction conversion ratio is 99%, filters and dezymotizes rear equal-volume ethyl acetate and extract 3 times, merges
Organic facies, sloughs solvent and obtains product 1.05g, purity 95%, ee value 99%.
Above-described embodiment only for technology design and the feature of the present invention are described, its object is to allow and is familiar with this skill
The personage of art will appreciate that present disclosure and is carried out, and can not limit the protection model of the present invention with this
Enclose, all equivalence changes made according to spirit of the invention or modification, all should contain the protection in the present invention
In the range of.
Claims (9)
- null1. (S)-5-chloro-2,The biological preparation method of 3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester，It is with 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester is substrate，This substrate is at biocatalyzer、In the presence of cofactor and cofactor regeneration system，Reduction reaction is occurred to generate (S)-5-chloro-2,3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester，It is characterized in that，Described biocatalyzer is monooxygenase，Described cofactor regeneration system includes glucose and glucose dehydrogenase，Described reduction reaction is 20-30 DEG C in temperature、PH be 7.0-8.0 water phase buffer solution in carry out，In initial action system，Described substrate 5-chloro-2,The concentration of 3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester is 15-25 mg/mL，Described monooxygenase and substrate 5-chloro-2,The mass ratio of 3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester is 1:1-20.
- (S) the most according to claim 1-5-chloro-2, the biological preparation method of 3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester, it is characterized in that, described monooxygenase is the combination of one or more in the monooxygenase that the trade mark is EW1531, EW1535, EW1536 or EW1538 purchased from the production of Suzhou Chinese biotechnology of enzymes company limited.
- (S) the most according to claim 2-5-chloro-2, the biological preparation method of 3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester, it is characterized in that, described monooxygenase is the monooxygenase that the trade mark is EW1535 produced purchased from Suzhou Chinese biotechnology of enzymes company limited.
- (S) the most according to claim 1-5-chloro-2, the biological preparation method of 3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester, it is characterized in that, in initial action system, the mass ratio of described glucose: glucose dehydrogenase: 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester is 15:1:10.
- (S) the most according to claim 1-5-chloro-2, the biological preparation method of 3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester, it is characterized in that, described cofactor is NADP, it is 1:1-100 with the mass ratio of 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester.
- The biological preparation method of (S)-MCIC the most according to claim 1, it is characterised in that described reaction is carried out under the conditions of cosolvent.
- (S) the most according to claim 6-5-chloro-2, the biological preparation method of 3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester, it is characterized in that, described cosolvent is the combination of one or more in hexamethylene, PEG400, polyethylene glycol 200, glycerol, toluene, ethylene glycol, Tween-60.
- The biological preparation method of (S)-MCIC the most according to claim 1, it is characterised in that described aqueous phase buffer solution is phosphate buffered solution.
- null(S) the most according to claim 1-5-chloro-2,The biological preparation method of 3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester，It is characterized in that，Specific implementation process is as follows: be sequentially added into described aqueous phase buffer solution in reaction vessel、Substrate 5-chloro-2,3-dihydro-1-oxo-1H-indenes-2-carboxylate methyl ester，After stirring，Add described monooxygenase、Cofactor、Glucose、Glucose dehydrogenase，Concussion reaction under 20-30 DEG C of temperature conditions，HPLC detects reaction process，When conversion ratio reaches 90-99%，After filtration is dezymotized，Add equal-volume ethyl acetate repeatedly to extract，Merge organic facies，(S)-5-chloro-2 is obtained after sloughing solvent,3-dihydro-2-hydroxyl-1-oxo-1H-indenes-2-carboxylate methyl ester product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110527646A (en) * | 2019-08-20 | 2019-12-03 | 浙江工业大学 | Tropical bacillus WZZ018 and its application |
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| CN110527646A (en) * | 2019-08-20 | 2019-12-03 | 浙江工业大学 | Tropical bacillus WZZ018 and its application |
| CN110527646B (en) * | 2019-08-20 | 2021-05-11 | 浙江工业大学 | Tropical bacillus WZZ018 and application thereof |
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