CN111961012B - Methionine derivative and application thereof - Google Patents
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- CN111961012B CN111961012B CN202010962365.8A CN202010962365A CN111961012B CN 111961012 B CN111961012 B CN 111961012B CN 202010962365 A CN202010962365 A CN 202010962365A CN 111961012 B CN111961012 B CN 111961012B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/18—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
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- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
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- C07B33/00—Oxidation in general
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
- C07C317/48—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
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Abstract
The invention relates to the technical field of chemical synthesis, and particularly discloses a methionine derivative and application thereof. The structure of the methionine derivative is shown as a formula (I). The methionine derivative provided by the invention is applied to an oxidation system as an oxidant, the hydroxyl of a reaction substrate is oxidized into corresponding aldehyde or ketone, no peculiar smell substance is generated in the reaction process, the yield of a target product is ensured, the reaction temperature can be effectively increased, the oxidation reaction can be normally carried out at the temperature higher than 0 ℃, the yield is higher, and the methionine derivative provided by the invention can be recycled for multiple times, so that the cost is saved, the energy is saved, the consumption is reduced, and the environment is protected.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a methionine derivative and application thereof.
Background
Oxidation is a type of reaction often involved in the field of organic synthesis, of which the Stevens oxidation and the Critical-gold oxidation are two important reaction types. Stevens oxidation (Swern oxidation): dimethyl sulfoxide is used as an oxidant, and an organic base (such as triethylamine) is used for cooperating with acyl chloride or acid anhydride at low temperature to oxidize primary alcohol or secondary alcohol into aldehyde and ketone, and the dimethyl sulfoxide is converted into dimethyl sulfide in the reaction process. Cori-gold oxidation (Corey-kim oxidation): the alcohol is treated by alkali under the action of N-chlorosuccinimide and dimethyl sulfide to obtain the corresponding aldehyde ketone. Dimethyl sulfide has unpleasant odor, and dimethyl sulfide is generated as a byproduct in the traditional Stevens oxidation reaction, and the Critical-metal oxidation reaction uses dimethyl sulfide as a reaction raw material, so that the traditional Stevens oxidation reaction and the Critical-metal oxidation reaction cause great pollution to the environment if being used for large-scale production, and are difficult to be applied to industrial production.
At present, a morpholine ring sulfur-containing compound is reported to be used as an oxidant for a Stevens oxidation reaction and a Critical-gold oxidation reaction instead of dimethyl sulfoxide or dimethyl sulfide, but the morpholine ring sulfur-containing compound is difficult to recycle after the reaction is finished (the recovery rate is less than 20%), so that the production cost is increased and the environment is polluted. There are also reports on the use of sulfur-containing resins as oxidizing agents for the Stevens oxidation reaction, but the reaction efficiency is low, the resin stability is poor and the price is expensive. Recently, sulfur-containing piperazine derivatives are reported to be used as oxidants of Stevens oxidation reaction and Critical-metal oxidation reaction, but the raw materials for preparing the sulfur-containing piperazine derivatives are high in cost, the reaction conditions are harsh, ultralow temperature reaction (-78 to-5 ℃) is required, the requirement on equipment is high, and the energy consumption is high. Therefore, it is necessary to develop a compound which is easily recycled, has good stability, high reaction efficiency and mild reaction conditions, and can be applied to the swern oxidation and the coriolis-mos reaction system on a large scale.
Disclosure of Invention
The invention provides a methionine derivative and application thereof, aiming at the problems of low recovery rate, poor stability, harsh reaction conditions and poor environmental protection of an oxidant in the existing Stevens oxidation and Critical-metal oxidation reaction system.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a methionine derivative has a structure shown in formula (I):
wherein X is S or sulfinyl;
R1is C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkoxysulfonyl, C1-C6 alkylsulfonyl, C5-C8 arylcarbonyl or
R3、R4Respectively H, hydroxyl, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl;
R2is hydroxy, N-methylpiperazinyl, pyridylamino, piperidinyl, C3-C6 cycloalkyloxy, C3-C6 halocycloalkyloxy, C1-C6 alkoxy or C1-C6 haloalkoxy.
Compared with the prior art, the methionine with wide source and low cost is selected as a lead compound, the amino and carboxyl contained in the methionine structure are used as derivative sites to obtain a series of methionine derivatives with rich structure types through structural modification, and the oxidation activity of the compounds on hydroxyl can be improved due to the existence of the amino and the carbonyl in the derivatives, so that the difficulty of oxidation reaction is reduced, and the oxidation reaction can be efficiently carried out under mild conditions; meanwhile, the prepared methionine derivative has high boiling point and good solubility in a solvent, and no odor is generated; in addition, carbonyl and substituted amino in the derivative are groups with larger polarity, so that the oxidation product and the methionine derivative are easier to separate by adjusting the pH value, the recovery rate of the methionine derivative is effectively improved, the methionine derivative has stable property and can be recycled for multiple times, the production cost is greatly reduced, and the industrial production is favorably realized.
Preferably, R1Is C1-C4 alkyl, C1-C3 haloalkyl, C1-C4 alkylcarbonyl, cyclopropyl, cyclopentyl or
Wherein R is3、R4H, C1-C4 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl respectively; r2Is hydroxy, N-methylpiperazinyl, pyridylamino, piperidinyl or C1-C4 alkoxy.
Preferred functional groups facilitate increasing the oxidation activity of the methionine derivative and facilitate its separation from the oxidation product.
Preferably, R1、R2、R3、R4Halogen in the substituent is Cl, Br or I.
Preferably, the compound of formula (I) of the present invention is prepared by the following steps:
when X is S, the compound of formula (I) is formed from methionine and R1-L or R1-O-R1The compounds shown are substituted by amino under alkaline condition, and then react with R2The compound shown as-H undergoes condensation reaction to obtain the methionine derivative, and the specific reaction equation is as follows, wherein R1、R2The functional groups are the same as above, and L is Cl, Br or I.
When X is S, the compound of formula (I) is formed from methionine and R1-L or R1-O-R1The compounds shown are substituted by amino under alkaline condition, and then react with R2The compound shown as-H undergoes condensation reaction and then undergoes oxidation reaction to obtain the methionine derivative, wherein the specific reaction equation is as follows, R1、R2The functional groups are the same as above, and L is Cl, Br or I.
The oxidant used in the oxidation reaction in the reaction process can be hydrogen peroxide, sodium hypochlorite, peroxybenzoic acid and peroxyacetic acid. The oxidation reaction can also be added with a catalytic amount of Fe-containing catalyst3+Or Co3+Of (e.g. FeCl)3、Co2O3) The conversion selectivity is improved, the generation of byproducts is reduced, and the purity of a target product is improved.
The invention also provides the application of the methionine derivative in an oxidation system, which is characterized in that: the compound shown in formula I is used as an oxidizing agent to oxidize the hydroxyl of a reaction substrate into corresponding aldehyde or ketone.
Preferably, the reaction substrate is abamectin.
Preferably, when X is S, the compound shown in the formula I is applied to a Critical-metal oxidation system, and the hydroxyl of a reaction substrate is oxidized into corresponding aldehyde or ketone under the condition of organic base and the combined action of an activator;
when X is sulfinyl, the compound shown in the formula I is applied to a Stevens oxidation system, and is used together with an activating agent under the condition of organic base to oxidize the hydroxyl of a reaction substrate into corresponding aldehyde or ketone.
The methionine derivative and an activating agent form an oxidation activator, and the hydroxyl of a reaction substrate is oxidized into a corresponding aldehyde or ketone structure under the action of an organic base.
Preferably, the compound shown in the formula I is used in an amount of 110-200% of the molar weight of the reaction substrate.
The preferred amount of the compound of formula I is that which ensures the total oxidative conversion of the target hydroxyl group in the reaction substrate to an aldehyde or ketone.
Preferably, the temperature of the oxidation reaction is 0-5 ℃.
The methionine derivative provided by the invention has stable property, still has higher stability at the optimal reaction temperature, and meanwhile, the optimal reaction temperature can not only improve the oxidation reaction efficiency, but also reduce the occurrence of side reactions and improve the yield and purity of a target product.
Preferably, in the Critical-Metal oxide system, the activator comprises chlorine gas, N-chlorosuccinimide, N-bromosuccinimide, a compound having an N, N '-dichlorourea structure, or a compound having an N, N' -dibromourea structure; in the Stevens oxidation system, the activating agent is acyl chloride or anhydride.
The compound containing the N, N '-dichloro or N, N' -dibromo urea structure can be selected from 1, 3-dichloro-5, 5-dimethyl hydantoin, 1, 3-dichloro-5-ethyl-5-methylimidazoline-2, 4-dione or tetrachloroglycoluril. The acid chloride or anhydride may be selected from phenyl phosphate diacid chloride, phosgene solids, oxalyl chloride or acetic anhydride.
The preferred activator can form an oxidation activator with the compound shown in the formula I, and the formed oxidation activator has high oxidation activity on hydroxyl and is beneficial to reducing the occurrence of side reactions.
Preferably, in the Critical-Metal oxide system and the Stevens oxidation system, the organic base comprises at least one of triethylamine, tetramethylethylenediamine, tributylamine, diisopropylethylamine, or pyridine.
Preferred organic bases facilitate increased deprotonation rates of the hydroxyl groups and the intermediates formed by the oxidizing active agents, thereby increasing the reaction rates.
Preferably, the molar ratio of the activating agent to the compound shown in the formula I is 0.5-1.5: 1, and the molar ratio of the organic base to the compound shown in the formula I is 1-2: 1.
The optimized ratio of the reaction substances can ensure that the oxidation reaction is fully performed under the condition of small using amount, thereby improving the yield of the target product.
Preferably, after the oxidation reaction is finished, adding water into the reaction system, adjusting the pH to 4-6 to separate a water phase from an organic phase, collecting the organic phase, evaporating the solvent, drying and concentrating to obtain an oxidation product; adjusting the pH value of the water phase to 8-10, extracting, collecting an organic phase, drying and concentrating to obtain the compound shown in the formula I.
After the methionine derivative provided by the invention is used for oxidation reaction, the methionine derivative can be recycled by adjusting the pH value of a system, so that the cost is saved, and the pollution to the environment is reduced.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
This example provides a methionine derivative, N- [1- (4-methylpiperazin-1-yl) -4- (methylthio) -1-carbonylbutan-2-yl ] acetamide, having the following formula Ia:
the preparation method comprises the following steps:
taking a clean reaction bottle, adding 14.9g of methionine and 40ml of glacial acetic acid, uniformly mixing, slowly dripping 10.2g of acetic anhydride, stirring and heating to 60 ℃, gradually dissolving the solid, keeping the temperature and stirring for reaction for 2 hours, and concentrating under reduced pressure at 60 ℃ to obtain 19g of white solid. The white solid is dissolved in 60g of dichloromethane, the temperature is reduced to 0 ℃, 12.2g of 4-Dimethylaminopyridine (DMAP) is added and stirred for 30min, 20g of N, N' -Dicyclohexylcarbodiimide (DCC) is added, then 10g of N-methylpiperazine is slowly dropped and stirred for reaction for 5h, the mixture is filtered, the filtrate is concentrated to be dry to obtain 30g of oily matter, 50g of ethyl acetate is added for crystallization, and 24.6g of white solid, namely N- [1- (4-methylpiperazin-1-yl) -4- (methylthio) -1-carbonylbutan-2-yl ] acetamide is obtained, the HPLC purity is 94.5%, and the yield is 85.1%.
The reaction equation is as follows.
1H NMR(400MHz,CDCl3)δ(ppm):8.11(s,1H),4.53(t,J＝3.0,1H),3.30(m,4H),2.60(t,J＝5.3,2H),2.27(m,4H),2.26(s,3H),2.14(s,3H),2.06(m,2H),1.84(s,3H)。
LC-MS[M+H]+:274.3949。
The compound is applied to a Coriolis-metal oxidation system to oxidize 5-allyloxycarbonyl ester abamectin B1The 4' hydroxyl in the structure (wherein, 5-allyloxycarbonyl ester abamectin B1Is abamectin B1Prepared by protecting 5-hydroxyl of initial raw materials), and specifically comprises the following steps:
(1) dispersing 10.0g of N-chlorosuccinimide (NCS) in 100mL of dichloromethane under the protection of nitrogen, cooling to 0 ℃, adding 13.6g of a compound N- [1- (4-methylpiperazin-1-yl) -4- (methylthio) -1-carbonylbutan-2-yl ] acetamide, and stirring at low temperature for 30 min;
(2) dissolving 37.8g of 5-allyloxycarbonyl ester abamectin B1 in 50mL of dichloromethane, dropwise adding into the step (1), keeping stirring for 30min at 0 ℃ after dropwise adding is finished for about 10 min;
(3) adding 5.8g of tetramethylethylenediamine into the step (2), keeping the temperature and stirring for 1.5h, and finishing the reaction;
(4) the reaction was warmed to room temperature, 100mL of water was added, stirred, and the pH was adjusted to 4 with 5 wt% hydrochloric acid solution, and the layers were separated, the organic phase was collected, the aqueous phase was retained, and the organic phase was dried over anhydrous magnesium sulfate and concentrated to give 37.0g of oxidized product with an HPLC purity of 90%. The yield is 88.4%;
(5) after 20 wt% sodium hydroxide solution was added to the aqueous phase in step (4) to adjust the pH to 10, 30mL of dichloromethane was added for extraction, and the organic phase was collected, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure at 50 ℃.
The recovered N- [1- (4-methylpiperazin-1-yl) -4- (methylthio) -1-carbonylbutan-2-yl ] acetamide was reused three times according to the above steps (1) to (5) to give a recovery of 92.1%.
Example 2
This example provides a sulfur-containing piperazine derivative, 2-benzoylamino-4- (methylsulfinyl) butyric acid, having the formula IIb:
the preparation method comprises the following steps:
taking a clean reaction bottle, adding 14.9g of methionine, 11.0g of triethylamine and 50mL of dichloromethane, stirring at room temperature for 30min, cooling to 0 ℃, then slowly dripping 14.0g of benzoyl chloride, stirring at the constant temperature for 2h, finishing the reaction, washing the reaction solution with 50mL of water, carrying out phase separation, and concentrating an organic phase to obtain 24.5g of white solid.
The white solid was added to 20g of water, 0.1g of FeCl was added3Cooling to 0 ℃, slowly dropping 12.5g of 30 wt% hydrogen peroxide solution, gradually dissolving the solid, keeping the temperature and stirring for reaction for 1h after adding, and concentrating to obtain 26.0g of white solid, namely 2-benzoylamino-4- (methylsulfinyl) butyric acid, wherein the HPLC purity is 97.5%, and the yield is 94.2%.
The reaction equation is as follows:
1H NMR(400MHz,CDCl3)δppm:11.0(s,1H),8.45(s,1H),8.03(m,2H),7.63(m,3H),4.53(t,J＝5.0,1H),2.57(t,J＝6.8,2H),2.50(s,3H),2.16(m,2H)。
LC-MS[M+H]+:270.3168。
the compound is used in a Stevens oxidation system to oxidize 5-allyloxycarbonyl ester abamectin B2The 4' hydroxyl in the structure specifically comprises the following steps:
(1) 9.5g of 5-allyloxycarbonyl ester abamectin B22.6g of tetramethylethylenediamine and 3.0g of 2-benzoylamino-4- (methylsulfinyl) butyric acid were dissolved in 40mL of dichloromethane at room temperature, stirred and cooled to 5 ℃;
(2) 4.0g of solid phosgene is dissolved in 10mL of dichloromethane and slowly dripped into the system in the step (1), the addition is finished for about 10min, and the mixture is stirred for 30min at the temperature of 5 ℃ after the dripping is finished, so that the reaction is finished;
(3) heating the reaction system to room temperature, adding 40mL of water, adjusting the pH value to 6 by using a 10 wt% HCl solution, carrying out phase separation, collecting an organic phase, retaining an aqueous phase, drying the organic phase by using anhydrous magnesium sulfate, and concentrating to obtain 9.21g of an oxidation product, wherein the HPLC purity is 91%, and the yield is 89%;
(4) adding 30 wt% sodium hydroxide solution into the water phase in the step (3), adjusting pH to 8, extracting with dichloromethane 25mL × 2 times, combining the organic phases, drying with anhydrous magnesium sulfate, concentrating under reduced pressure at 50 deg.C, adding 10mL water into the residue, cooling to 0 deg.C, and adding 30 wt% H dropwise2O2The solution (11.3 g) was stirred at the same temperature for 1 hour and then concentrated under reduced pressure to give 2.92g of 2-benzoylamino-4- (methylsulfinyl) butanoic acid as a compound with an HPLC purity of 98.2% and a recovery rate of 98.1%.
The recovered 2-benzoylamino-4- (methylsulfinyl) butyric acid was reused three times according to the above steps (1) to (5), and the recovery rate was 92.8%.
Examples 3 to 11
A series of methionine derivatives as shown in Table 1 below were prepared by reacting methionine with the raw materials 1 and 2 shown in the table, using different reaction raw materials according to the methods of example 1 and example 2. The reaction solvent and the conditions of reaction temperature, time, etc. during the reaction can be adjusted by those skilled in the art.
Wherein the II compound is a product obtained by continuously oxidizing the I compound. The oxidant used in the oxidation reaction can be selected from hydrogen peroxide, sodium hypochlorite, peroxybenzoic acid or peroxyacetic acid. The oxidation reaction can also be added with a catalytic amount of Fe-containing catalyst3+Or Co3+Of (e.g. FeCl)3、Co2O3)。
TABLE 1
5-allyloxycarbonyl-ester-based Avermectin B of Table 1 according to the procedure of example 1 above, the procedure was followed1Oxidation reaction of the hydroxyl group of (a); the compound of class II of Table 1 was subjected to 5-allyloxycarbonyl ester abamectin B according to the procedure of example 2 above, operating according to the Stevens oxidation reaction2Oxidation reaction of the hydroxyl group of (a); the yield of the prepared avermectin oxide and the yield of the methionine derivative after being recycled three times are shown in table 2.
TABLE 2
The HPLC content detection method of the methionine derivative in the above example is as follows: c18 column, flow rate: 1.0mL/min, detection wavelength: 210nm, mobile phase: methanol-water (volume ratio 80:20), isocratic elution.
The HPLC content detection method of the avermectin oxide comprises the following steps:
a chromatographic column: c18 chromatography column, detection wavelength: 245nm, flow rate: 1.4mL/min, mobile phase: acetonitrile-water (86: 14 by volume, 0.02% (v/v) trifluoroacetic acid in water) and isocratic elution.
In conclusion, the methionine derivative provided by the invention is applied to an oxidation system as an oxidant, the hydroxyl of a reaction substrate is oxidized into corresponding aldehyde or ketone, no peculiar smell substance is generated in the reaction process, the yield of a target product is ensured, the reaction temperature can be effectively increased, the oxidation reaction can be normally carried out at the temperature higher than 0 ℃, the yield is high, and the methionine derivative provided by the invention can be recycled for multiple times, so that the cost is saved, the energy is saved, the consumption is reduced, and the environment is protected.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (8)
1. The application of the methionine derivative with the structure shown as the formula (I) in an oxidation system is characterized in that the compound shown as the formula (I) is used as an oxidant to oxidize hydroxyl of a reaction substrate into corresponding aldehyde or ketone;
（Ⅰ）
wherein X is S or sulfinyl;
R1is C1-C6 alkyl, C1-C6 haloalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C1-C6 alkylcarbonyl, C1-C6 alkoxycarbonyl, C1-C6 alkoxysulfonyl, C1-C6 alkylsulfonyl, C5-C8 arylcarbonyl or
，R3、R4Respectively H, hydroxyl, C1-C6 alkyl, C1-C6 haloalkyl or C3-C6 cycloalkyl;
R2is hydroxy, N-methylpiperazinyl, pyridylamino, piperidinyl, C3-C6 cycloalkyloxy, C3-C6 halocycloalkyloxy, C1-C6 alkoxy or C1-C6 haloalkoxy;
when X is S, the compound shown in the formula (I) is applied to a Critical-metal oxidation system, and the hydroxyl of a reaction substrate is oxidized into corresponding aldehyde or ketone under the condition of organic alkali and the combined action of an activator;
when X is sulfinyl, the compound shown in the formula (I) is applied to a Stevens oxidation system, and under the condition of organic base, the compound and an activating agent act together to oxidize the hydroxyl of a reaction substrate into corresponding aldehyde or ketone;
in the Cride-metal oxidation system, the activator is chlorine, N-chlorosuccinimide, N-bromosuccinimide, a compound containing an N, N '-dichlorourea structure or a compound containing an N, N' -dibromourea structure; in the Stevens oxidation system, the activating agent is acyl chloride or anhydride.
2. Use of methionine derivatives in oxidation systems according to claim 1 wherein R1Is C1-C4 alkyl, C1-C3 haloalkyl, C1-C4 alkylcarbonyl, cyclopropyl, cyclopentyl or
Wherein R is3、R4H, C1-C4 alkyl, C1-C3 haloalkyl or C3-C6 cycloalkyl respectively; r2Is hydroxy, N-methylpiperazinyl, pyridylamino, piperidinyl or C1-C4 alkoxy.
3. The use of a methionine derivative according to claim 1 in an oxidation system wherein the reaction substrate is abamectin.
4. The use of methionine derivative according to claim 3 in oxidation system, wherein the compound of formula (I) is used in an amount of 110 to 200% by mole based on the reaction substrate.
5. The use of a methionine derivative according to claim 3 in an oxidation system wherein the temperature of the oxidation reaction is 0-5 ℃.
6. The use of a methionine derivative according to claim 1 in oxidation systems, wherein the organic base comprises at least one of triethylamine, tetramethylethylenediamine, tributylamine, diisopropylethylamine or pyridine in both the Crui-MOS and Stevens oxidation systems.
7. The use of the methionine derivative according to claim 1 in an oxidation system, wherein the molar ratio of the activating agent to the compound of formula (i) is 0.25 to 3:1, and the molar ratio of the organic base to the compound of formula (i) is 0.5 to 2.5: 1.
8. The application of the methionine derivative in an oxidation system according to claim 1, wherein after the oxidation reaction is finished, water is added into the reaction system, the pH is adjusted to 4-6, so that a water phase and an organic phase are separated, the organic phase is collected, and the oxidation product is obtained after evaporation, solvent removal, drying and concentration; and adjusting the pH value of the water phase to 8-10, extracting, collecting an organic phase, and drying and concentrating to obtain the compound shown in the formula (I).
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