CN105272848B - A kind of preparation method of trans dextrorotation DV chrysanthemumic acid - Google Patents
A kind of preparation method of trans dextrorotation DV chrysanthemumic acid Download PDFInfo
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- CN105272848B CN105272848B CN201410324209.3A CN201410324209A CN105272848B CN 105272848 B CN105272848 B CN 105272848B CN 201410324209 A CN201410324209 A CN 201410324209A CN 105272848 B CN105272848 B CN 105272848B
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Abstract
The present invention proposes a kind of preparation method of trans dextrorotation DV chrysanthemumic acid, including：The trans DL DV chrysanthemumic acid of 200g is added in 1000~2000g mother liquors under agitation, pH value is adjusted to 6.5~8.2 with alkali, trans DL DV chrysanthemumic acid salting liquids are generated；90~110g resolving agents are dissolved in water under agitation, pH value is adjusted to 2~5 by acid adding, obtain the resolving agent aqueous solution；The resolving agent aqueous solution is added drop-wise in trans DL DV chrysanthemumic acid salting liquids under agitation, time for adding 1~3 hour, generation includes the solution of solid double salt；200~400g release agents are added into the solution comprising solid double salt under agitation, stir to isolate solid double salt particle and aqueous phase；Acid adding makes the pH value for the aqueous phase liquid isolated be adjusted to 2~4 under agitation, forms solid and the aqueous solution, the solid is trans dextrorotation DV chrysanthemumic acid.The present invention solves the problem of existing method for splitting prepares trans dextrorotation DV chrysanthemumic acid production procedures length, complex process, high cost.
Description
Technical field
The present invention relates to a kind of preparation method of trans dextrorotation DV chrysanthemumic acid (also known as DV chrysanthemumic acid), i.e., by way of fractionation
Realize preparation process.
Background technology
Trans dextrorotation DV chrysanthemumic acid is the important intermediate for producing pyrethroid insecticides transfluthrin Chiral pesticide.
Because environmentally friendly cry day is high, pesticide control law rule are gradually improved, in addition the restriction of the factors such as market and benefit so that using single
Isomers is planted, efficient, low toxicity, low cost is developed, turns into the trend of Agrochemicals without poisoning Chiral pesticide, and how to obtain hand
Property pesticide intermediate is the key of synthesis of chiral agricultural chemicals, also determines the production technology and cost of Pesticidal products.
As the trans dextrorotation DV chrysanthemumic acid system domestic blank product of intermediate, only Bayer Bitterfeld GmbH (Bayer) is public in the world
The problem of taking charge of and produced using the method for chemical resolution, but there is production procedure length, complex process, high cost.
The content of the invention
The present invention proposes a kind of preparation method of trans dextrorotation DV chrysanthemumic acid, and the trans right side is prepared for solving existing method for splitting
The problem of revolving DV chrysanthemumic acid production procedures length, complex process, high cost.
The technical proposal of the invention is realized in this way：
A kind of preparation method of trans dextrorotation DV chrysanthemumic acid, comprises the following steps：
Step 1：The trans DL DV chrysanthemumic acid of 200g, is added to by the preparation of trans DL DV chrysanthemumic acid salting liquids under agitation
In 1000~2000g mother liquors, with saponification, pH value is adjusted to 6.5~8.2, trans DL DV chrysanthemumic acid salting liquids are made；
Step 2：The preparation of the resolving agent aqueous solution, is dissolved in water and by acid adding by 90~110g resolving agents under agitation
PH value is adjusted to 2~5, the resolving agent aqueous solution is made；
Step 3：Split, the resolving agent aqueous solution made from step 2 is added drop-wise to trans DL made from step 1 under agitation
In DV chrysanthemumic acid salting liquids, it is 1~3 hour to control time for adding, and the solution for including solid double salt is made；
Step 4：Grain is tied, 200~400g separation is added into the obtained solution comprising solid double salt of step 3 under agitation
Agent, makes the solution of solid double salt be separated into solid double salt particle and aqueous phase, and by solid double salt particle and aqueous phase separation；
Step 5：Aqueous phase is acidified, and acid adding makes the pH value for the aqueous phase that step 4 isolates be adjusted to 2~4 under agitation, consolidate
Body and the aqueous solution, the solid are trans dextrorotation DV chrysanthemumic acid.
In preferred scheme, above-mentioned preparation method also includes：
Step 6：200~400g water is added in the solid double salt particle isolated under agitation to step 4, and acid adding makes
PH value is adjusted to 2~4, obtains aqueous phase and organic phase, and by aqueous phase and organic phase separation.
In preferred scheme, above-mentioned preparation method also includes：The aqueous solution that step 5 is obtained is anti-as next group is prepared
The mother liquor used during formula dextrorotation DV chrysanthemumic acid.
In preferred scheme, the mother liquor is water.
In preferred scheme, above-mentioned preparation method also includes：The aqueous phase liquid that step 6 is isolated is used as preparing next group
The resolving agent used during trans dextrorotation DV chrysanthemumic acid.
In preferred scheme, the release agent is toluene or petroleum ether.
In preferred scheme, the alkali is ammoniacal liquor or the NaOH aqueous solution.
In preferred scheme, the acid used in step 2 and step 5 is hydrochloric acid.
In preferred scheme, the resolving agent is D- (-)-D-pHPG carbethoxy hydrochloride.
The present invention relates to the key for preparing Chiral pesticide transfluthrin, propargyl chloride chrysanthemum ester, cypermethrin and fenvalerate
Intermediate trans dextrorotation DV chrysanthemumic acid.Trans dextrorotation DV chrysanthemumic acid production is not only met needed for agricultural production, while being produced to China's agricultural chemicals
The development of industry, regional economic develop the innovative development of series of products related to other and extension will also imitate with great economy
Benefit and social benefit.The present invention solve existing method for splitting prepare trans dextrorotation DV chrysanthemumic acid production procedures length, complex process, into
The problem of this is high.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
In the examples below used trans dextrorotation DV chrysanthemumic acid be No. CAS be 55701-03-6 DV chrysanthemumic acid (3- (2,
2-Dichloroethenyl) -2,2-dimethylcyclopropanecarboxylic acid), also known as trans dextrorotation chrysanthemum
Acid, DV chrysanthemums ester or 3- (2,2- dichloroethylenes) -2,2- dimethyl cyclopropane carboxylic acids.Used trans DL DV chrysanthemumic acid is also known as
For trans DL chrysanthemumic acid (trans l chicoric acid and trans-D-chrysanthemic acid exist simultaneously).
A kind of preparation method for trans dextrorotation DV chrysanthemumic acid that the present invention is provided, comprises the following steps：
Step 1：The trans DL DV chrysanthemumic acid of 200g, is added to by the preparation of trans DL DV chrysanthemumic acid salting liquids under agitation
It is saponification with ammoniacal liquor or the NaOH aqueous solution etc. in 1000~2000g mother liquors, pH value is adjusted to 6.5~8.2, is made trans mixed
Revolve DV chrysanthemumic acid salting liquids；
Wherein, trans DL DV chrysanthemumic acid is that solid is water insoluble, and trans DL DV chrysanthemates are generated after adding the alkali such as ammoniacal liquor
It is water-soluble, generate trans DL DV chrysanthemumic acid salting liquids.
Step 2：The preparation of the resolving agent aqueous solution, is dissolved in water and by acid adding by 90~110g resolving agents under agitation
PH value is adjusted to 2~5, the resolving agent aqueous solution is made.
Step 3：Split, the resolving agent aqueous solution made from step 2 is added drop-wise to trans DL made from step 1 under agitation
In DV chrysanthemumic acid salting liquids, it is 1~3 hour to control time for adding, and the solution for including solid double salt is made；
Wherein, solid double salt be trans left-handed DV chrysanthemumic acid with resolving agent combination, but solid double salt is thick, is difficult
Separated with the aqueous solution, be that this present embodiment employs separation method as described in step 4.
Step 4：Grain is tied, 200~400g separation is added into the obtained solution comprising solid double salt of step 3 under agitation
Agent, makes the solution of solid double salt be separated into solid double salt particle and aqueous phase, and by solid double salt particle and aqueous phase separation.
Wherein, release agent is petroleum ether or toluene；After step 4, trans dextrorotation DV chrysanthemumic acid dissolves in a salt form
In water, trans left-handed, dextrorotation DV chrysanthemumic acid separation is realized.
Step 5：Aqueous phase is acidified, and acid adding makes the pH value for the aqueous phase that step 4 isolates be adjusted to 2~4 under agitation, consolidate
Body and the aqueous solution, the solid are trans dextrorotation DV chrysanthemumic acid.
Wherein, trans dextrorotation DV chrysanthemumic acid contents, can be according to the more of resolving agent addition between 90~99% in solid
It is few to adjust trans dextrorotation DV chrysanthemumic acid contents.
The mother liquor that above-mentioned steps are used is water, in order to ensure that trans dextrorotation DV chrysanthemumic acid is not unrestrained after step 1 to 5 processing
Take, the aqueous solution that can also obtain step 5 is used as preparing the mother liquor used during the trans dextrorotation DV chrysanthemumic acid of next group.
In order to obtain trans left-handed DV chrysanthemumic acid or reuse resolving agent, following steps can be performed：
Step 6：200~400g water is added in the solid double salt particle isolated under agitation to step 4, and acid adding makes
PH value is adjusted to 2~4, obtains aqueous phase and organic phase, and by aqueous phase and organic phase separation.
Wherein, the aqueous phase that step 6 is isolated is the resolving agent aqueous solution, when can be used as preparing the trans dextrorotation DV chrysanthemumic acid of next group
The resolving agent used.Organic phase is trans left-handed DV chrysanthemumic acid and release agent, can be dissolved in petroleum ether.So as to make trans left-handed DV
Chrysanthemumic acid liquid and resolving agent separation.Invalid body (the trans left-handed DV chrysanthemums of mass ratio more than 95% are included after organic phase product drying
Acid).
In addition, it is hydrochloric acid that acid adding (acidifying), which adjusts the acid used during pH value,.
The feature of the present invention is as follows：
It is domestic that trans DL DV chrysanthemumic acid is split using D- (-)-D-pHPG carbethoxy hydrochloride first；
It is domestic first to be separated double salt and another single rotator using the method for knot grain, greatly save labor intensity and improvement
Production environment；Domestic general separation method is to centrifuge, and there is workload greatly, the shortcoming of environment difference；
Various raw material consumptions are low in the present invention, and the whole operation process in cost, production process of the present invention that reduces all is closed
Operation, is lost small；The unit consumption of resolving agent and toluene all reaches less than 5%, the yield of trans dextrorotation DV chrysanthemumic acid 95~99% (Gu
Mass percent shared by trans dextrorotation DV chrysanthemumic acid in body product)；
Environmental compatibility is stronger than other trans dextrorotation DV chrysanthemumic acid processing technologys：Due to high income, Recycling Mother Solution is applied mechanically, so
Waste discharge is few, and the wastewater flow rate of one ton of finished product is between 3~4 tons, along with waste water salt content is high, chemical oxygen demand of waste water
(COD) it is low, between 1500~3000ppm；
Energy consumption is low：Whole split process is all normal-temperature operation, and temperature can between 0~40 DEG C, it is not necessary to which cooling rises
Steam is needed to heat when warm process, only end product precipitation solution.
Specific embodiment is set forth below to illustrate that the resolving agent used in the present invention, embodiment is D- (-)-para hydroxybenzene
Glycine ethyl ester hydrochloride.
Embodiment：
Add water 1200g into 2000ml there-necked flasks, puts into trans DL DV chrysanthemumic acid 200g, opens stirring, and ammoniacal liquor is added dropwise and adjusts pH
It is worth 7.2；
Resolving agent 100g is added into 1000ml there-necked flasks, add water 350g, opening stirring, resolving agent is dissolved as resolving agent molten
PH value is adjusted to 3.6 by liquid, plus hydrochloric acid.
Agent solution will be split under agitation to be added drop-wise in above-mentioned 2000ml there-necked flasks, 35 DEG C of operation temperature, time for adding 85
Minute, completion of dropwise addition is incubated 20 minutes, adds toluene 300g, solid particle is formed after 18 minutes.Standing separates aqueous phase A10, then
The 500g that adds water washs solid particle, separates aqueous phase B 10.By in aqueous phase A10, the another there-necked flask of aqueous phase B 10, it is acidified pH
Value is adjusted to 2.5 and obtains trans dextrorotation DV chrysanthemumic acid and water, and suction filtration obtains wet product 102g, and drying obtains finished product 91g (reaction bulb bottle walls
It is upper probably to also have 5-8g attachments, can be handled in lower batch of preparation process).Trans dextrorotation DV chrysanthemumic acid quality percentage in 91g finished products
It is 96.3% than content.
Add water 200g into the solid particle by washing, and stirring is lower to be added dropwise hydrochloric acid, and adjustment pH value is 2.8, stratification,
Obtain resolving agent aqueous phase a10 and organic phase a20.Again toward the 100g washings that add water in organic phase a20, static layering obtains resolving agent water
Phase b10 and organic phase b20.By resolving agent aqueous phase a10, resolving agent aqueous phase b10 be transferred to another there-necked flask (can be with it is above-mentioned
There-necked flask different reaction bulb) in, stir 5 minutes, obtain resolving agent aqueous phase liquid.Resolving agent aqueous phase liquid product is 420ml, through surveying
Optically-active, calculates 97.4g containing resolving agent inside resolving agent aqueous phase liquid.Trans left-handed DV chrysanthemumic acid is through adding water in organic phase a20 and b20
Alkaline saponification is transferred to aqueous phase, then acidified processing obtains trans left-handed DV chrysanthemumic acid, and it is straight that resolving agent aqueous phase liquid can be used as resolving agent
Female connector is used in the preparation of the trans dextrorotation DV chrysanthemumic acid of next group.Trans left-handed DV chrysanthemumic acid wet product 101g is obtained, is after drying
It is 98.3% to contain trans left-handed DV chrysanthemumic acid mass percent in 97.1g, this 97.1g product.
Lot number is as follows for 201403008 to 201403013 product preparation process：
1st, the preparation of the product of lot number 201403008：
Add water 1000g into 2000ml there-necked flasks, puts into trans DL DV chrysanthemumic acid 200g, opens stirring, and ammoniacal liquor is added dropwise and adjusts pH
It is worth 6.5；
Resolving agent 90g is added into 1000ml there-necked flasks, add water 300g, opening stirring, resolving agent is dissolved as resolving agent molten
Liquid, acid adding adjustment pH value is 2.
Agent solution will be split under agitation to be added drop-wise in above-mentioned 2000ml there-necked flasks, 0 DEG C of operation temperature, 60 points of time for adding
Clock, completion of dropwise addition is incubated 18 minutes, adds toluene 200g, forms solid particle.Standing separates aqueous phase A11, adds water washing solid
Body particle, separates aqueous phase B 11.Aqueous phase A11, aqueous phase B 11 are transferred in another there-necked flask, is acidified and pH value is adjusted to 2
Trans dextrorotation DV chrysanthemumic acid and water are obtained, suction filtration obtains wet product, and drying obtains trans dextrorotation DV chrysanthemumic acid matter in finished product 101.2g, finished product
It is 95.5% to measure degree.
Added water into the solid particle by washing, stirring is lower to be added dropwise hydrochloric acid, and adjustment pH value is 2, and static layering is torn open
Divide agent aqueous phase a11 and organic phase a21.Again toward the washing that adds water in organic phase a21, static layering obtains resolving agent aqueous phase b11 with having
Machine phase b21.Resolving agent aqueous phase a11, resolving agent aqueous phase b11 are transferred in another there-necked flask, stirs 3 minutes, obtains resolving agent
Aqueous phase liquid.Trans left-handed DV chrysanthemumic acid is transferred to aqueous phase through the alkaline saponification that adds water in organic phase a21 and b21, then acidified handles
To trans left-handed DV chrysanthemumic acid, resolving agent aqueous phase liquid is used as the preparation that resolving agent directly set uses the trans dextrorotation DV chrysanthemumic acid of next group
In.Trans left-handed DV chrysanthemumic acid wet product is obtained, is 96.2g after drying, trans left-handed DV chrysanthemumic acid quality percentage is contained in this 96.2g product
Than for 99.2%.
2nd, the preparation of the product of lot number 201403009：
Add water 1300g into 2000ml there-necked flasks, puts into trans DL DV chrysanthemumic acid 200g, opens stirring, and ammoniacal liquor is added dropwise and adjusts pH
It is worth 6.8；
Resolving agent 100g is added into 1000ml there-necked flasks, add water 350g, opening stirring, resolving agent is dissolved as resolving agent molten
Liquid, acid adding adjustment pH value is 2.2.
Agent solution will be split under agitation to be added drop-wise in above-mentioned 2000ml there-necked flasks, 20 DEG C of operation temperature, time for adding 90
Minute, completion of dropwise addition is incubated 19 minutes, adds toluene 210g, forms solid particle afterwards.Standing separates aqueous phase A12, adds water and washes
Solid particle is washed, aqueous phase B 12 is separated.Aqueous phase A12, aqueous phase B 12 are transferred in another there-necked flask, is acidified and adjusts pH value
Trans dextrorotation DV chrysanthemumic acid and water are obtained to 2.2, suction filtration obtains wet product, and drying obtains trans dextrorotation DV chrysanthemums in finished product 98.0g, finished product
Sour mass percentage content is 95.6%.
Added water into the solid particle by washing, stirring is lower to be added dropwise hydrochloric acid, and adjustment pH value is 2.1, and static layering is obtained
Resolving agent aqueous phase a12 and organic phase a22.Again toward the washing that adds water in organic phase a22, static layering obtain resolving agent aqueous phase b12 with
Organic phase b22.Resolving agent aqueous phase a12, resolving agent aqueous phase b12 are transferred in another there-necked flask, stirs 4 minutes, must split
Agent aqueous phase liquid.Trans left-handed DV chrysanthemumic acid is transferred to aqueous phase, then acidified processing through the alkaline saponification that adds water in organic phase a22 and b22
Trans left-handed DV chrysanthemumic acid is obtained, resolving agent aqueous phase liquid is used as the preparation that resolving agent directly set uses the trans dextrorotation DV chrysanthemumic acid of next group
In.Trans left-handed DV chrysanthemumic acid wet product is obtained, is 99.0g after drying, trans left-handed DV chrysanthemumic acid quality percentage is contained in this 99.0g product
Than for 95.6%.
3rd, the preparation of the product of lot number 201403010：
Add water 1400g into 2000ml there-necked flasks, puts into trans DL DV chrysanthemumic acid 200g, opens stirring, and ammoniacal liquor is added dropwise and adjusts pH
It is worth 7.3；
Resolving agent 98g is added into 1000ml there-necked flasks, add water 380g, opening stirring, resolving agent is dissolved as resolving agent molten
Liquid, acid adding adjustment pH value is 2.6.
Agent solution will be split under agitation to be added drop-wise in above-mentioned 2000ml there-necked flasks, 24 DEG C of operation temperature, time for adding 110
Minute, completion of dropwise addition is incubated 20 minutes, adds petroleum ether 240g, forms solid particle afterwards.Standing separates aqueous phase A13, adds water
Solid particle is washed, aqueous phase B 13 is separated.Aqueous phase A13, aqueous phase B 13 are transferred in another there-necked flask, is acidified and adjusts pH value
Whole to obtain trans dextrorotation DV chrysanthemumic acid and water to 2.6, suction filtration obtains wet product, and drying obtains trans dextrorotation DV in finished product 98.5g, finished product
Chrysanthemumic acid mass percentage content is 96.3%.
Added water into the solid particle by washing, stirring is lower to be added dropwise hydrochloric acid, and adjustment pH value is 2.4, and static layering is obtained
Resolving agent aqueous phase a13 and organic phase a23.Again toward the washing that adds water in organic phase a23, static layering obtain resolving agent aqueous phase b13 with
Organic phase b23.Resolving agent aqueous phase a13, resolving agent aqueous phase b13 are transferred in another there-necked flask, stirs 5 minutes, must split
Agent aqueous phase liquid.Trans left-handed DV chrysanthemumic acid is transferred to aqueous phase, then acidified processing through the alkaline saponification that adds water in organic phase a23 and b23
Trans left-handed DV chrysanthemumic acid is obtained, resolving agent aqueous phase liquid is used as the preparation that resolving agent directly set uses the trans dextrorotation DV chrysanthemumic acid of next group
In.Trans left-handed DV chrysanthemumic acid wet product is obtained, is 96.5g after drying, trans left-handed DV chrysanthemumic acid quality percentage is contained in this 96.5g product
Than for 96.3%.
4th, the preparation of the product of lot number 201403011：
Add water 1750g into 2000ml there-necked flasks, puts into trans DL DV chrysanthemumic acid 200g, opens stirring, NaOH is added dropwise water-soluble
Liquid adjusts pH value to 7.6；
Resolving agent 100g is added into 1000ml there-necked flasks, add water 400g, opening stirring, resolving agent is dissolved as resolving agent molten
Liquid, acid adding adjustment pH value is 3.8.
Agent solution will be split under agitation to be added drop-wise in above-mentioned 2000ml there-necked flasks, 28 DEG C of operation temperature, time for adding 130
Minute, completion of dropwise addition is incubated 21 minutes, adds petroleum ether 280g, forms solid particle afterwards.Standing separates aqueous phase A14, adds water
Solid particle is washed, aqueous phase B 14 is separated.Aqueous phase A14, aqueous phase B 14 are transferred in another there-necked flask, is acidified and adjusts pH value
Whole to obtain trans dextrorotation DV chrysanthemumic acid and water to 2.9, suction filtration obtains wet product, and drying obtains trans dextrorotation DV in finished product 98.4g, finished product
Chrysanthemumic acid mass percentage content is 95.5%.
Added water into the solid particle by washing, stirring is lower to be added dropwise hydrochloric acid, and adjustment pH value is 2.8, and static layering is obtained
Resolving agent aqueous phase a14 and organic phase a24.Again toward the washing that adds water in organic phase a24, static layering obtain resolving agent aqueous phase b14 with
Organic phase b24.Resolving agent aqueous phase a14, resolving agent aqueous phase b14 are transferred in another there-necked flask, stirs 3 minutes, must split
Agent aqueous phase liquid.Trans left-handed DV chrysanthemumic acid is transferred to aqueous phase, then acidified processing through the alkaline saponification that adds water in organic phase a24 and b24
Trans left-handed DV chrysanthemumic acid is obtained, resolving agent aqueous phase liquid is used as the preparation that resolving agent directly set uses the trans dextrorotation DV chrysanthemumic acid of next group
In.Trans left-handed DV chrysanthemumic acid wet product is obtained, is 98.7g after drying, trans left-handed DV chrysanthemumic acid quality percentage is contained in this 98.7g product
Than for 95.5%.
5th, the preparation of the product of lot number 201403012：
Add water 1580g into 2000ml there-necked flasks, puts into trans DL DV chrysanthemumic acid 200g, opens stirring, NaOH is added dropwise water-soluble
Liquid adjusts pH value to 7.9；
Resolving agent 102g is added into 1000ml there-necked flasks, add water 430g, opening stirring, resolving agent is dissolved as resolving agent molten
Liquid, acid adding adjustment pH value is 4.5.
Agent solution will be split under agitation to be added drop-wise in above-mentioned 2000ml there-necked flasks, 36 DEG C of operation temperature, time for adding 150
Minute, completion of dropwise addition is incubated 25 minutes, adds toluene 330g, forms solid particle afterwards.Standing separates aqueous phase A15, adds water and washes
Solid particle is washed, aqueous phase B 15 is separated.Aqueous phase A15, aqueous phase B 15 are transferred in another there-necked flask, is acidified and adjusts pH value
Trans dextrorotation DV chrysanthemumic acid and water are obtained to 3.3, suction filtration obtains wet product, and drying obtains trans dextrorotation DV chrysanthemums in finished product 96.6g, finished product
Sour mass percentage content is 97.3%.
Added water into the solid particle by washing, stirring is lower to be added dropwise hydrochloric acid, and adjustment pH value is 3.5, and static layering is obtained
Resolving agent aqueous phase a15 and organic phase a25.Again toward the washing that adds water in organic phase a25, static layering obtain resolving agent aqueous phase b15 with
Organic phase b25.Resolving agent aqueous phase a15, resolving agent aqueous phase b15 are transferred in another there-necked flask, stirs 5 minutes, must split
Agent aqueous phase liquid.Trans left-handed DV chrysanthemumic acid is transferred to aqueous phase, then acidified processing through the alkaline saponification that adds water in organic phase a25 and b25
Trans left-handed DV chrysanthemumic acid is obtained, resolving agent aqueous phase liquid is used as the preparation that resolving agent directly set uses the trans dextrorotation DV chrysanthemumic acid of next group
In.Trans left-handed DV chrysanthemumic acid wet product is obtained, is 102g after drying, trans left-handed DV chrysanthemumic acid mass percent is contained in this 102g product
For 94.8%.
6th, the preparation of the product of lot number 201403013：
Add water 2000g into 2000ml there-necked flasks, puts into trans DL DV chrysanthemumic acid 200g, opens stirring, NaOH is added dropwise water-soluble
Liquid adjusts pH value to 8.2；
Resolving agent 120g is added into 1000ml there-necked flasks, add water 500g, opening stirring, resolving agent is dissolved as resolving agent molten
Liquid, acid adding adjustment pH value is 5.
Agent solution will be split under agitation to be added drop-wise in above-mentioned 2000ml there-necked flasks, 40 DEG C of operation temperature, time for adding 180
Minute, completion of dropwise addition is incubated 22 minutes, adds petroleum ether 400g, forms solid particle afterwards.Standing separates aqueous phase A16, adds water
Solid particle is washed, aqueous phase B 16 is separated.Aqueous phase A16, aqueous phase B 16 are transferred in another there-necked flask, is acidified and adjusts pH value
Whole to obtain trans dextrorotation DV chrysanthemumic acid and water to 4, suction filtration obtains wet product, and drying obtains trans dextrorotation DV in finished product 102.8g, finished product
Chrysanthemumic acid mass percentage content is 96.2%.
Added water into the solid particle by washing, stirring is lower to be added dropwise hydrochloric acid, and adjustment pH value is 4, and static layering is torn open
Divide agent aqueous phase a16 and organic phase a26.Again toward the washing that adds water in organic phase a26, static layering obtains resolving agent aqueous phase b16 with having
Machine phase b26.Resolving agent aqueous phase a16, resolving agent aqueous phase b16 are transferred in another there-necked flask, stirs 6 minutes, obtains resolving agent
Aqueous phase liquid.Trans left-handed DV chrysanthemumic acid is transferred to aqueous phase through the alkaline saponification that adds water in organic phase a26 and b26, then acidified handles
To trans left-handed DV chrysanthemumic acid, resolving agent aqueous phase liquid is used as the preparation that resolving agent directly set uses the trans dextrorotation DV chrysanthemumic acid of next group
In.Trans left-handed DV chrysanthemumic acid wet product is obtained, is 98.1g after drying, trans left-handed DV chrysanthemumic acid quality percentage is contained in this 98.1g product
Than for 96.2%.
Above-described embodiment collects for such as following table：
Table 1:
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God is with principle, and any modification, equivalent substitution and improvements made etc. should be included in the scope of the protection.
Claims (6)
1. a kind of preparation method of trans dextrorotation DV chrysanthemumic acid, it is characterised in that comprise the following steps：
Step 1：The preparation of trans DL DV chrysanthemumic acid salting liquids, the trans DL DV chrysanthemumic acid of 200g is added to 1000 under agitation~
In 2000g mother liquors, with saponification, pH value is adjusted to 6.5~8.2, trans DL DV chrysanthemumic acid salting liquids are made；The mother liquor is
Water；
Step 2：The preparation of the resolving agent aqueous solution, is dissolved in water and by acid adding by pH by 90~110g resolving agents under agitation
Value is adjusted to 2~5, and the resolving agent aqueous solution is made；The resolving agent is D- (-)-D-pHPG carbethoxy hydrochloride；
Step 3：Split, the resolving agent aqueous solution made from step 2 is added drop-wise to trans DL DV chrysanthemums made from step 1 under agitation
In acid salt solution, it is 1~3 hour to control time for adding, and the solution for including solid double salt is made；
Step 4：Grain is tied, 200~400g release agents are added into the obtained solution comprising solid double salt of step 3 under agitation,
The solution of solid double salt is set to be separated into solid double salt particle and aqueous phase, and by solid double salt particle and aqueous phase separation；The separation
Agent is toluene or petroleum ether；
Step 5：Aqueous phase is acidified, and acid adding makes the pH value for the aqueous phase that step 4 isolates be adjusted to 2~4 under agitation, obtain solid and
The aqueous solution, the solid is trans dextrorotation DV chrysanthemumic acid.
2. the preparation method of a kind of trans dextrorotation DV chrysanthemumic acid according to claim 1, it is characterised in that also include：
Step 6：200~400g water is added in the solid double salt particle isolated under agitation to step 4, and acid adding makes pH value
It is adjusted to 2~4, obtains aqueous phase and organic phase, and by aqueous phase and organic phase separation.
3. the preparation method of a kind of trans dextrorotation DV chrysanthemumic acid according to claim 1, it is characterised in that also include：Will step
Rapid 5 aqueous solution obtained are used as preparing the mother liquor used during the trans dextrorotation DV chrysanthemumic acid of next group.
4. the preparation method of a kind of trans dextrorotation DV chrysanthemumic acid according to claim 2, it is characterised in that also include：Will step
The rapid 6 aqueous phase liquid isolated are used as preparing the resolving agent used during the trans dextrorotation DV chrysanthemumic acid of next group.
5. the preparation method of a kind of trans dextrorotation DV chrysanthemumic acid according to claim 1, it is characterised in that the alkali is ammoniacal liquor
Or the NaOH aqueous solution.
6. the preparation method of a kind of trans dextrorotation DV chrysanthemumic acid according to claim 1, it is characterised in that step 2 and step 5
The middle acid used is hydrochloric acid.
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| CN101830795A (en) * | 2010-04-08 | 2010-09-15 | 山东理工大学 | Preparation method of chrysanthemic acid with high optical purity |
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