CN101613268B - Method for manufacturing rich reverse type first chrysanthemic acid - Google Patents
Method for manufacturing rich reverse type first chrysanthemic acid Download PDFInfo
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- CN101613268B CN101613268B CN2009100127603A CN200910012760A CN101613268B CN 101613268 B CN101613268 B CN 101613268B CN 2009100127603 A CN2009100127603 A CN 2009100127603A CN 200910012760 A CN200910012760 A CN 200910012760A CN 101613268 B CN101613268 B CN 101613268B
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Abstract
The invention provides a method for manufacturing a rich reverse type first chrysanthemic acid. The method is characterized by comprising the following steps: using a racemization (+/-) first chrysanthemic acid with a purity of 93-99 percent and a forward inverse ratio between 3/97 and 20/80 as the material; crystallizing by means of melt crystallization at a temperature of 39.7-51 DEG C to obtain a rich reverse type first chrysanthemic acid with a forward inverse ratio of 1.5/98.5-9/91; and sweating, filtering and crystallizing the rich reverse type first chrysanthemic acid to obtain the rich reverse type first chrysanthemic acid with high purity, wherein the sweating temperature is 1-3 DEG C higher than the crystallizing temperature.
Description
Technical field
The present invention relates to rich reverse type first chrysanthemic acid, a kind of technology with fusion-crystallization manufactured rich reverse type first chrysanthemic acid is provided especially.
Background technology
First chrysanthemumic acid (claiming chrysanthemumic acid again, English name Chrysanthemic acid) is the important intermediate compound that the acid of synthetic pyrethroid agricultural chemicals is partly formed.First chrysanthemumic acid, promptly 2,2-dimethyl--3-3 (2-methyl isophthalic acid-propenyl) cyclopropane-carboxylic acid is shown below
Because of there being two chiral carbon atoms on its cyclopropane ring, R (+) and two kinds of configurations of S (-) are therefore arranged, also have cis and trans two kinds of isomeries, have four kinds of isomer.Sour portion as pyrethroid pesticide forms, first chrysanthemumic acid of different isomerization body, and its desinsection is renderd a service and is assumed a marked difference.As far as cis and transconfiguration, reverse type first chrysanthemic acid is renderd a service apparently higher than cis first chrysanthemumic acid.
At present, the most frequently used method for preparing reverse type first chrysanthemic acid be from four kinds of isomer of first chrysanthemumic acid with effective body anti--chrysanthemumic acid isolates, and makes the highest R (+) of effectiveness-anti--chrysanthemumic acid through splitting again.
Now, synthesizing efficient, the low toxicity chirality agricultural chemicals that is of value to environment protection has become important development trend.
Summary of the invention
The method of manufacture that the purpose of this invention is to provide a kind of rich reverse type first chrysanthemic acid, this method is high to the selectivity of purpose product rich reverse type first chrysanthemic acid, and on producing, can implement easily.
The invention provides a kind of method of manufacture of rich reverse type first chrysanthemic acid, it is characterized in that:
Raw material: to adopt purity be 93-99% along inverse ratio is raw material at 3/97 to 20/80 racemization (±) first chrysanthemumic acid;
Method of manufacture: utilize the crystallization under 39.7～51 ℃ of TRs of fusion-crystallization method, making along inverse ratio is the rich reverse type first chrysanthemic acid of 1.5/98.5～9/91.
The rich reverse type first chrysanthemic acid sweating that makes is filtered, and recrystallize generates highly purified rich reverse type first chrysanthemic acid afterwards, and wherein sweating temperature need be higher than 1 ℃～3 ℃ of Tcs.
The mechanism that the impurity of crystallized product exists mainly is solid solubleness, and the position that impurity exists is mainly the lattice dot matrix.Mechanism according to the impurity existence; The impurity that is adopted removes technology and is " sweating+recrystallize ": after the crystal growth, recrystallize is filtered in sweating under sweating temperature, and sweating temperature is wanted a little higher than Tc; Can obtain highly purified rich reverse type first chrysanthemic acid, and guarantee the crystalline high cis-to-trans ratio.
For two-component system, the phasor of this system can be drawn in temperature and concentration coordinate when constant voltage operation.This technology belongs to " eutectic type system ", and its phasor is as shown in Figure 1:
In system, can form " eutectic system " (the Eutectic System) with minimum Tc, it is an A and B blended solid by a certain percentage.Point A is the crystallization solidification value of pure substance A, and some B is the Tc of substance B.Curve A E and BE represent that the different composition mixtures with B of A separate out Tc.Eutectoid point E is two intersections of complex curve, and the liquid phase with corresponding component all forms solid mixture with same composition at this point.
Method provided by the present invention is different from solution crystallization; The Tc of fusion-crystallization depends on the crystalline material fusing point; Melt crystallization temperature and racemization (±) first chrysanthemumic acid are closely related along inverse ratio, and the suitable inverse ratio value of racemization (±) first chrysanthemumic acid is big more, and Tc is low more; More little along the inverse ratio value, Tc is high more; The suitable inverse ratio of racemization (±) first chrysanthemumic acid and Tc are to concern (Tc and raw material are as shown in Figure 2 along the graph of a relation of inverse ratio) one to one.By 20/80 to 3/97, Tc is controlled between 39.7～51 ℃ along inverse ratio.And the form of mold is simple, can be still formula or tower.
The method of manufacture of a kind of rich reverse type first chrysanthemic acid provided by the present invention is characterized in that: be not higher than fused raw material racemization (±) first chrysanthemumic acid fusion extremely fully under 60 ℃ of temperature.
The method of manufacture of a kind of rich reverse type first chrysanthemic acid provided by the present invention is characterized in that: crystallization time is 2～7 hours.
The method of manufacture of a kind of rich reverse type first chrysanthemic acid provided by the present invention is characterized in that: solid content remains between 40～50% during crystallization, with the convenient material that shifts.
The fusion-crystallization method that the present invention adopted is different from solution crystallization, and process is solvent-free, does not relate to the problem of dissolution with solvents loss and solvent reclaiming, clean process, and production cost is low, and yield is high.In industry, be prone to realize.
Description of drawings
Fig. 1 is an eutectic type system phasor;
Fig. 2 is the graph of a relation of Tc and the suitable inverse ratio of raw material.
Embodiment
Accurate weighing racemization (±) first chrysanthemumic acid, 60 ℃ of complete fusions down, stirred crystallization 2～7hr at a slow speed under the Tc of correspondence; And insulation is filtered; The filter pocket chuck heats up and makes the crystal sweating then, while hot liquid is extruded, and crystal is shifted in cooling; Can get the rich reverse type first chrysanthemic acid of high cis-to-trans ratio, filtrating can be carried out fusion-crystallization again.
Claims (4)
1. the method for manufacture of a rich reverse type first chrysanthemic acid is characterized in that:
Raw material: to adopt purity be 93-99% along inverse ratio is raw material at 3/97 to 20/80 racemization (±) first chrysanthemumic acid;
Method of manufacture: utilize the crystallization under 39.7 ~ 51 ℃ of TRs of fusion-crystallization method, making along inverse ratio is the rich reverse type first chrysanthemic acid of 1.5/98.5 ~ 9/91;
The rich reverse type first chrysanthemic acid sweating that makes is filtered, and recrystallize generates highly purified rich reverse type first chrysanthemic acid afterwards, and wherein sweating temperature need be higher than 1 ℃ ~ 3 ℃ of Tcs.
2. according to the method for manufacture of the described rich reverse type first chrysanthemic acid of claim 1, it is characterized in that: be not higher than fused raw material racemization (±) first chrysanthemumic acid fusion extremely fully under 60 ℃ of temperature.
3. according to the method for manufacture of the described rich reverse type first chrysanthemic acid of claim 1, it is characterized in that: crystallization time is 2 ~ 7 hours.
4. according to the method for manufacture of the described rich reverse type first chrysanthemic acid of claim 1, it is characterized in that: solid content remains between 40 ~ 50% during crystallization.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100127603A CN101613268B (en) | 2009-07-28 | 2009-07-28 | Method for manufacturing rich reverse type first chrysanthemic acid |
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| CN2009100127603A CN101613268B (en) | 2009-07-28 | 2009-07-28 | Method for manufacturing rich reverse type first chrysanthemic acid |
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| CN101613268A CN101613268A (en) | 2009-12-30 |
| CN101613268B true CN101613268B (en) | 2012-06-13 |
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| CN109694321B (en) * | 2017-10-24 | 2021-09-14 | 中国石油化工股份有限公司 | Method for preparing high-purity cyclohexanecarboxylic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0068736A1 (en) * | 1981-06-18 | 1983-01-05 | Stauffer Chemical Company | Resolution of d,1-trans-chrysanthemic acid L-(-)-ephedrine |
| CN1058956A (en) * | 1991-04-08 | 1992-02-26 | 南开大学 | The fractionation of cis-chrysanthemic acid |
| CN1298862A (en) * | 1999-10-18 | 2001-06-13 | 住友化学工业株式会社 | Prepn. of (+)-trans-chrysanthemic acid |
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2009
- 2009-07-28 CN CN2009100127603A patent/CN101613268B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0068736A1 (en) * | 1981-06-18 | 1983-01-05 | Stauffer Chemical Company | Resolution of d,1-trans-chrysanthemic acid L-(-)-ephedrine |
| CN1058956A (en) * | 1991-04-08 | 1992-02-26 | 南开大学 | The fractionation of cis-chrysanthemic acid |
| CN1298862A (en) * | 1999-10-18 | 2001-06-13 | 住友化学工业株式会社 | Prepn. of (+)-trans-chrysanthemic acid |
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