CN113979860B - 2,4-dichlorophenoxyacetic acid crystal and preparation method and application thereof - Google Patents
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- C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
- C07C59/70—Ethers of hydroxy-acetic acid, e.g. substitutes on the ring
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- A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
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Abstract
The invention provides a 2,4-dichlorophenoxyacetic acid crystal and a preparation method and application thereof, wherein the 2,4-dichlorophenoxyacetic acid crystal is in a II crystal form, and the 2,4-dichlorophenoxyacetic acid crystal has characteristic peaks at diffraction angles expressed by 2 theta angles of 10.44 +/-0.2 degrees, 13.69 +/-0.2 degrees, 16.19 +/-0.2 degrees, 20.48 +/-0.2 degrees, 21.08 +/-0.2 degrees, 24.06 +/-0.2 degrees, 31.21 +/-0.2 degrees, 31.80 +/-0.2 degrees and 32.79 +/-0.2 degrees by X-ray powder diffraction measured by Cu-Kalpha radiation. The 2,4-dichlorophenoxyacetic acid crystal has good elastic mechanical properties, so that the crystal has the potential of being further developed into novel functional drug materials and nonlinear optical materials.
Description
Technical Field
The invention relates to a 2,4-dichlorophenoxyacetic acid crystal and a preparation method and application thereof, in particular to a new crystal form of 2,4-dichlorophenoxyacetic acid and application thereof in the field of specific elasticity, and belongs to the technical field of pharmaceutical chemistry.
Background
2,4-dichlorphenoxyacetic acid (2,4-D) is an auxin analogue, is used as a plant growth regulator and herbicide, has an action mechanism similar to that of plant hormone, and can promote or inhibit the growth of certain organs by interfering the hormone balance in plants, destroying the metabolism of nucleic acid and protein, and enabling stems and leaves of weeds to twist, stem bases to become thick, and stem cracks to be formed. 2,4-dichlorophenoxyacetic acid has two activities of stimulating and inhibiting plant growth, and the herbicidal effect is a strong inhibition expression. In agricultural production, the stimulation is used for improving the quality and yield of products, and the inhibition is mainly used as a herbicide. The chemical structure of 2,4-dichlorophenoxyacetic acid is as follows:
there is only one of 2,4-dichlorophenoxyacetic acid crystal forms reported in the literature, smith, G. et al 1976 reported that 2,4-dichlorophenoxyacetic acid crystal form I has a single crystal structure under 295K (J.chem.Soc., perkin Trans.1976,7, 791-792), 2011
L. et al report a single crystal structure of 2,4-dichlorophenoxyacetic acid form I (Organic Chemistry International,2011,1-5) at 90K with similar unit cell parameters, which can be considered as a form.
Wherein 2,4-dichlorophenoxyacetic acid which is a substance which is an organic crystal in addition to its use as a pesticide. The research on the mechanical properties of organic crystals is relatively popular, and there are currently few reports on single-component organic crystals having mechanical properties. Based on the method, the screening of the 2,4-dichlorophenoxyacetic acid new crystal form is tried by optimizing the process or changing the crystallization conditions, and whether the application field can be widened is judged.
Disclosure of Invention
Aiming at the defects of the existing crystal form in the aspect of mechanical property, the invention provides a novel needle-shaped 2,4-dichlorophenoxyacetic acid crystal with an elastic function.
The invention aims to provide a method for stably preparing 2,4-dichlorophenoxyacetic acid crystals with elastic function.
In order to achieve the purpose, the invention provides a 2,4-dichlorophenoxyacetic acid crystal, wherein the 2,4-dichlorophenoxyacetic acid crystal is in a II crystal form, and the 2,4-dichlorophenoxyacetic acid crystal has characteristic peaks at diffraction angles expressed by 2 theta angles of 10.44 +/-0.2 degrees, 13.69 +/-0.2 degrees, 16.19 +/-0.2 degrees, 20.48 +/-0.2 degrees, 21.08 +/-0.2 degrees, 24.06 +/-0.2 degrees, 31.21 +/-0.2 degrees, 31.80 +/-0.2 degrees and 32.79 +/-0.2 degrees by X-ray powder diffraction measured by using Cu-Ka radiation.
Preferably, the 2,4-dichlorophenoxyacetic acid crystal also has characteristic peaks at diffraction angles expressed in 2 theta angle of 9.12 + -0.2 °, 18.06 + -0.2 °, 18.50 + -0.2 °, 25.09 + -0.2 °, 26.32 + -0.2 °, 27.91 + -0.2 ° and 36.21 + -0.2 °.
The 2,4-dichlorophenoxyacetic acid crystal obtained by the invention has better elasticity, so that the application range of the 2,4-dichlorophenoxyacetic acid crystal is widened.
The X-ray powder diffraction pattern of the 2,4-dichlorophenoxyacetic acid crystal obtained by using a D/MAX-2500X-ray diffractometer (Rigaku) diffractometer is shown in figure 1. The measurement conditions were as follows: cu K alpha radiation
100mA and40kV light source, step length of 0.02 degree, scanning speed of 8 degrees/min, scanning range of 2-40 degrees, room temperature of 20 degrees.
The invention adopts a Rigaku Saturn 70CCD diffracometer single crystal diffractometer to measure the single crystal structure of 2,4-dichlorophenoxyacetic acid crystal under 100K, and uses a graphite monochromator Mo K alpha ray
Data were collected by means of multislice scans, and were corrected by means of ShelXL (Sheldrick, 2015) packages. The space group is determined according to the extinction rule of the system and verified by the fine-trimming result. All crystal structures were solved by direct methods using ShelXL (Sheldrick, 2015), the structures were corrected by full matrix least squares using the program ShelXL-2018/3 (Sheldrick 2018), and hydrogen atom coordinates were added by theoretical calculation. The single crystal structure of 2,4-D crystal form II is obtained, the unit cell is monoclinic, the space group is I12/a 1, a =19.7556 (12) b =4.1464 (3) c =22.8692 (16), alpha =90, beta =105.177 (7), gamma =90, the unit cell volume
The crystal structure is shown in figure 2, the unit cell stacking is shown in figure 3, 2,4-dichlorophenoxyacetic acidDimers are formed among molecules, the dimers are connected through weak intermolecular interaction of C-H-O to form a one-dimensional chain, and adjacent chains are stacked and extended through weak interaction. The crystallographic parameters of the 2,4-dichlorophenoxyacetic acid crystals are shown in Table 1 below.
TABLE 1
The spectrum of the thermogram of 2,4-dichlorophenoxyacetic acid crystal of the present invention is shown in fig. 4, with exothermic peaks at onset point 58.77 ℃ and peak 68.61 ℃, and endothermic peaks at onset point 138.96 ℃ and peak 140.15 ℃.
A2,4-dichlorophenoxyacetic acid sample is heated to 90 ℃ at a rate of 10 ℃/K, and the sample naturally cooled to room temperature is subjected to PXRD detection, and the obtained PXRD spectrum is compared with a spectrum calculated by a crystal form I single crystal and a powder XRD spectrum, as shown in figure 5. The PXRD spectrogram shows that a 2,4-dichlorophenoxyacetic acid sample heated to 90 ℃ is basically consistent with the calculated spectrogram of the crystal form I single crystal, namely, the novel crystal form II is heated to 90 ℃ and then is transformed into the crystal form I.
The 2,4-dichlorophenoxyacetic acid crystal is a long needle crystal habit, and the length-width ratio of the long needle crystal habit is (80-500) to 1.
The second purpose of the invention is to provide a preparation method of 2,4-dichlorophenoxyacetic acid crystal, which comprises the following steps:
adding 2,4-dichlorophenoxyacetic acid methanol solution into aqueous solution with dissolved polymer, and performing elution crystallization to obtain 2,4-dichlorophenoxyacetic acid crystal; the polymer comprises any one or the combination of at least two of polyvinylpyrrolidone (PVP), vinylpyrrolidone and vinyl acetate copolymer (PVPVA) or sodium polyacrylate.
Preferably, the number average molecular weight of the polyvinylpyrrolidone is 8000-80000, the number average molecular weight of the copolymer of the vinylpyrrolidone and the vinyl acetate is 8000-100000, and the number average molecular weight of the sodium polyacrylate is < 10000.
Preferably, the methanol solution of 2,4-dichlorophenoxyacetic acid has a concentration of 4-10wt%.
Preferably, the addition amount of water in the aqueous solution dissolved with the polymer is 80-120g, based on 1g of 2,4-dichlorophenoxyacetic acid in 2,4-dichlorophenoxyacetic acid methanol solution.
Preferably, the concentration of the aqueous solution in which the polymer is dissolved is 1 to 10% by weight.
Preferably, the step obtains the 2,4-dichlorophenoxyacetic acid crystal II form in a long needle shape, and the crystal can be bent and can rebound to an original shape under a certain mechanical pressure, namely has elasticity.
As described above, the present invention has excellent effects in that:
1. the preparation method of the 2,4-dichlorophenoxyacetic acid crystal II is simple, and a pure metastable crystal form can be obtained by adding a specific polymer, so that crystal transformation is inhibited.
2. The 2,4-dichlorophenoxyacetic acid crystal II can be bent under the action of mechanical pressure, and the crystal can rebound to the original shape after the mechanical pressure is removed, so that the crystal has mechanical elasticity.
Drawings
FIG. 1 is an X-ray powder diffraction Pattern (PXRD) of 2,4-dichlorophenoxyacetic acid crystals prepared in example 1;
FIG. 2 is a diagram showing the structure of a monomer obtained by single crystal analysis of 2,4-dichlorophenoxyacetic acid crystals prepared in example 1;
FIG. 3 is a schematic representation of the packing cell of 2,4-dichlorophenoxyacetic acid crystals prepared in example 1;
FIG. 4 is a DSC of 2,4-dichlorophenoxyacetic acid crystals prepared in example 1;
FIG. 5 is an X-ray powder diffraction Pattern (PXRD) of a sample prepared in example 1 and having 2,4-dichlorophenoxyacetic acid crystals heated to 90 ℃;
FIG. 6 is a diagram showing the elastic bending process of 2,4-dichlorophenoxyacetic acid crystals prepared in example 1.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and its several details are capable of modifications and variations in various respects, all without departing from the spirit of the invention.
Example 1
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 10g of methanol solution, adding Wen Di of the solution chamber into water in which 1 per thousand of PVP is dissolved, dissolving out crystals, filtering to separate solid, and vacuum drying the solid at 40 ℃ to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 1 was characterized by X-ray powder diffraction (abbreviated as "XRD") and the spectrum is shown in fig. 1. The characteristic peaks in XRD pattern at 2 theta (+ -0.200 deg.) are located at 10.44, 13.69, 16.19, 18.06, 20.48, 21.08, 24.06, 25.09, 27.91, 31.80 and 32.79 degrees. Specifically, the diffraction pattern summary of 2,4-D form II in fig. 1 is shown in table 2:
TABLE 2
| 2θ(°) | Relative Strength (%) | 2θ(°) | Relative Strength (%) |
| 9.12 | 9.8 | 24.06 | 65.1 |
| 10.44 | 28.2 | 25.09 | 33.7 |
| 13.69 | 27.5 | 26.32 | 23.1 |
| 16.19 | 57.6 | 27.91 | 29.0 |
| 18.06 | 26.7 | 31.21 | 19.6 |
| 18.50 | 22.7 | 31.80 | 79.6 |
| 20.48 | 92.9 | 32.79 | 24.7 |
| 21.08 | 100.0 | 36.21 | 17.3 |
The monomer structure of 2,4-dichlorophenoxyacetic acid crystal obtained by single crystal analysis is shown in fig. 2. FIG. 3 shows the cell stacking diagram of 2,4-triclosan acetic acid crystal of this example, as can be seen from FIG. 3: 5363 and dimers are formed among 2,4-dichlorophenoxyacetic acid molecules, the dimers are connected through weak intermolecular interaction of C-H-O to form one-dimensional chains, and adjacent chains are stacked and extended through weak interaction.
FIG. 4 shows a Differential Scanning Calorimetry (DSC) pattern of 2,4-D form II of this example, which shows that there is a small exothermic peak at 68 deg.C, in order to verify whether this exothermic peak is a transgranular peak, X-ray powder diffraction is performed on a sample after heating 2,4-dichlorophenoxyacetic acid crystal to 90 deg.C, the pattern is shown in FIG. 5, and FIG. 5 shows that the XRD pattern of the sample after heating to 90 deg.C is consistent with form I, i.e. the form II is transgranular to form I.
FIG. 6 is a diagram showing the elastic bending process of 2,4-dichlorophenoxyacetic acid crystal, wherein the crystal is clamped by a forceps and then pressed towards the middle of the crystal by a metal needle to be elastically bent and can be rapidly rebounded after the external force is removed, which shows that the crystal has better elasticity.
Example 2
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 10g of methanol solution, adding Wen Di of the solution chamber into water in which 10 per thousand of PVP is dissolved, dissolving out crystals, filtering to separate solid, and vacuum drying the solid at 40 ℃ to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 2 was subjected to the same test method as in example 1, and it was found that the obtained product was the same crystal form II as in example 1, and the DSC spectrum was also substantially the same as in example 1.
Bending test is carried out on the 2,4-dichlorophenoxyacetic acid crystal obtained in example 2, and the crystal is bent under the pressure action of a metal needle, the action of withdrawing force is carried out, and the crystal is recovered, so that the crystal has better elasticity.
Example 3
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 15g of methanol solution, adding Wen Di of the solution chamber into water in which 1 per thousand of PVP is dissolved, dissolving out crystals, filtering to separate solid, and vacuum drying the solid at 40 ℃ to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 3 was subjected to the same test method as in example 1, and it was found that the obtained product was the same crystal form II as in example 1, and the DSC spectrum was also substantially the same as in example 1.
Bending test is carried out on the 2,4-dichlorophenoxyacetic acid crystal obtained in example 3, and the crystal is bent under the pressure action of a metal needle, the action of withdrawing force is carried out, and the crystal is recovered, so that the crystal has better elasticity.
Example 4
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 25g of methanol solution, adding Wen Di of the solution chamber into water in which 1 per thousand of PVP is dissolved, dissolving out crystals, filtering to separate solid, and vacuum drying the solid at 40 ℃ to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 4 was subjected to the same test method as in example 1, and it was found that the obtained product was the same crystal form II as in example 1, and the DSC spectrum was also substantially the same as in example 1.
Bending test is carried out on the 2,4-dichlorophenoxyacetic acid crystal obtained in example 4, and the crystal is bent under the pressure action of a metal needle, the action of withdrawing force is carried out, and the crystal is recovered, so that the crystal has better elasticity.
Example 5
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 15g of methanol solution, adding Wen Di of the solution chamber into water in which 1 per mill of polymer sodium polyacrylate is dissolved, dissolving out crystals, filtering and separating solids, and drying the solids at 40 ℃ in vacuum to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 5 was subjected to the same test method as in example 1, and it was found that the obtained product was the same crystal form II as in example 1, and the DSC spectrum was also substantially the same as in example 1.
Bending test is carried out on the 2,4-dichlorophenoxyacetic acid crystal obtained in example 5, and the crystal is bent under the pressure action of a metal needle, the action of withdrawing force is carried out, and the crystal is recovered, so that the crystal has better elasticity.
Example 6
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 15g of methanol solution, adding Wen Di of the solution chamber into water in which 10 per mill of polymer sodium polyacrylate is dissolved, dissolving out crystals, filtering and separating solids, and drying the solids at 40 ℃ in vacuum to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 6 was subjected to the same test method as in example 1, and it was found that the obtained product was the same crystal form II as in example 1, and the DSC spectrum was also substantially the same as in example 1.
Bending test is carried out on the 2,4-dichlorophenoxyacetic acid crystal obtained in example 6, and the crystal is bent under the pressure action of a metal needle, the action of withdrawing force is carried out, and the crystal is recovered, so that the crystal has better elasticity.
Example 7
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 15g of methanol solution, adding Wen Di of the solution chamber into water in which 1 per thousand of polymer PVPVA is dissolved, dissolving out crystals, filtering and separating solids, and drying the solids at 40 ℃ in vacuum to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 7 was subjected to the same test method as in example 1, and it was found that the obtained product was the same crystal form II as in example 1, and the DSC spectrum was substantially the same as in example 1.
Bending test is carried out on the 2,4-dichlorophenoxyacetic acid crystal obtained in example 7, and the crystal is bent under the pressure action of a metal needle, the action of withdrawing force is carried out, and the crystal is recovered, so that the crystal has better elasticity.
Example 8
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 15g of methanol solution, adding Wen Di of the solution chamber into water in which 10 per mill of polymer PVPVA is dissolved, dissolving out crystals, filtering and separating solids, and drying the solids at 40 ℃ in vacuum to constant weight to obtain 2,4-dichlorophenoxyacetic acid crystals.
The 2,4-dichlorophenoxyacetic acid crystal obtained in example 8 was subjected to the same test method as in example 1, and it was found that the obtained product was the same crystal form II as in example 1, and the DSC spectrum was also substantially the same as in example 1.
Bending test is carried out on the 2,4-dichlorophenoxyacetic acid crystal obtained in the example 8, and the crystal is found to be bent under the pressure action of a metal needle, the action of withdrawing force is carried out, and the crystal is restored to the original shape, so that the crystal has better elasticity.
Comparative example 1
Dissolving 1g of 2, 4-dichlorophenoxyacetic acid in 15g of methanol solution, dripping the solution into water without a polymer additive at room temperature, separating out crystals by dissolution, filtering to separate a solid, and drying the solid at 40 ℃ in vacuum to constant weight to obtain the solid.
No additive is added in the comparative example, and the result shows that the crystal form II is subjected to solution-mediated crystal transformation and is transformed into the crystal form I, and the obtained solid is mixed crystal. Indicating that the selected polymer additive has the effect of inhibiting the crystal transformation.
Claims (16)
1. The 2,4-dichlorophenoxyacetic acid crystal is characterized in that the 2,4-dichlorophenoxyacetic acid crystal is in a II crystal form;
the 2,4-dichlorophenoxyacetic acid crystal has 2% X-ray powder diffraction measured by Cu-Ka radiationθThe diffraction angle expressed by the angle has characteristic peaks at 10.44 +/-0.2 degrees, 13.69 +/-0.2 degrees, 16.19 +/-0.2 degrees, 20.48 +/-0.2 degrees, 21.08 +/-0.2 degrees, 24.06 +/-0.2 degrees, 31.21 +/-0.2 degrees, 31.80 +/-0.2 degrees and 32.79 +/-0.2 degrees.
2. The 2,4-dichlorophenoxyacetic acid crystal according to claim 1, wherein said 2,4-dichlorophenoxyacetic acid crystal further has characteristic peaks at diffraction angles, in terms of 2 Θ, of 9.12 ± 0.2 °, 18.06 ± 0.2 °, 18.50 ± 0.2 °, 25.09 ± 0.2 °, 26.32 ± 0.2 °, 27.91 ± 0.2 ° and 36.21 ± 0.2 °.
3. The 2,4-dichlorophenoxyacetic acid crystal of claim 1, wherein the crystalline form of 2,4-dichlorophenoxyacetic acid crystal is monoclinic and space group isI 12/a1, unit cell parameter ofa= 19.7556(12)， b= 4.1464(3) c=22.8692(16)，α=90°，β=105.177(7)°，γ=90 °, cell volume 1808.0 (2) a 3 。
4. The 2,4-dichlorophenoxyacetic acid crystal according to claim 1, wherein dimers are formed between 2,4-dichlorophenoxyacetic acid molecules, the dimers are linked by weak intermolecular interaction to form one-dimensional chains, and adjacent chains are stacked and extended by weak interaction.
5. The 2,4-dichlorophenoxyacetic acid crystal according to claim 1, wherein said 2,4-dichlorophenoxyacetic acid crystal has a differential scanning calorimetry DSC profile with an exothermic peak at 68.61 ± 5 ℃ and an endothermic peak at 140.15 ± 5 ℃.
6. The 2,4-dichlorophenoxyacetic acid crystal according to claim 1, wherein said 2,4-dichlorophenoxyacetic acid crystal is a long needle habit, said long needle habit having an aspect ratio of (80-500): 1.
7. The 2,4-dichlorophenoxyacetic acid crystal according to claim 1, wherein said 2,4-dichlorophenoxyacetic acid crystal is bent by mechanical pressure and rebounds to its original shape when the mechanical pressure is removed.
8. The method of producing 2,4-dichlorophenoxyacetic acid crystals as claimed in any of claims 1-7, comprising the steps of:
adding 2,4-dichlorophenoxyacetic acid methanol solution into aqueous solution with dissolved polymer, and performing elution crystallization to obtain 2,4-dichlorophenoxyacetic acid crystal; the polymer comprises any one or the combination of at least two of polyvinylpyrrolidone, vinylpyrrolidone and vinyl acetate copolymer or sodium polyacrylate.
9. The method of claim 8, wherein the concentration of 2,4-dichlorophenoxyacetic acid in methanol is 4-10wt%.
10. The method of claim 8 wherein the amount of water added to the aqueous solution of dissolved polymer is 80 to 120g, based on the amount of 2,4-dichlorophenoxyacetic acid added to a solution of 2,4-dichlorophenoxyacetic acid in methanol being 1 g.
11. The method of claim 8, wherein the concentration of the aqueous solution having the polymer dissolved therein is 1 to 10wt ‰.
12. The method according to claim 8, wherein the polyvinylpyrrolidone has a number average molecular weight of 8000 to 80000, the vinylpyrrolidone/vinyl acetate copolymer has a number average molecular weight of 8000 to 100000, and the sodium polyacrylate has a number average molecular weight of not higher than 10000.
13. The method according to claim 8, further comprising subjecting the crystallized material to solid-liquid separation, washing and drying.
14. The method according to claim 13, wherein the solid-liquid separation is performed by filtration.
15. The method for preparing the nano-particles according to claim 13, wherein the drying is carried out under vacuum, the temperature of the vacuum drying is 35-50 ℃, the vacuum degree is 0.1 MPa, and the drying time is 8 h.
16. Use of the 2,4-dichlorophenoxyacetic acid crystal according to any of claims 1 to 7 in the preparation of herbicides, plant growth regulators.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04173764A (en) * | 1990-11-07 | 1992-06-22 | Mitsubishi Kasei Corp | Production of 1,3-phenylenedioxydiacetic acid |
| CN1252048A (en) * | 1997-02-12 | 2000-05-03 | Basf公司 | Dicarboxylic acid crystallizates |
| RO116395B1 (en) * | 1997-07-28 | 2001-01-30 | Sc Oltchim Sa | Process for purifying 2,4-dichlorophenoxyacetic acid |
| CN104276944A (en) * | 2014-09-15 | 2015-01-14 | 天津科技大学 | Method for controlling continuous reaction crystal size of 2,4-dichlorphenoxyacetic acid |
| CN108467343A (en) * | 2018-04-03 | 2018-08-31 | 湘潭大学 | The preparation method of 2,4- dichlorphenoxyacetic acids |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB607113A (en) * | 1946-03-13 | 1948-08-25 | Boots Pure Drug Co Ltd | Improvements relating to the manufacture of halogenated carboxylic acids |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04173764A (en) * | 1990-11-07 | 1992-06-22 | Mitsubishi Kasei Corp | Production of 1,3-phenylenedioxydiacetic acid |
| CN1252048A (en) * | 1997-02-12 | 2000-05-03 | Basf公司 | Dicarboxylic acid crystallizates |
| RO116395B1 (en) * | 1997-07-28 | 2001-01-30 | Sc Oltchim Sa | Process for purifying 2,4-dichlorophenoxyacetic acid |
| CN104276944A (en) * | 2014-09-15 | 2015-01-14 | 天津科技大学 | Method for controlling continuous reaction crystal size of 2,4-dichlorphenoxyacetic acid |
| CN108467343A (en) * | 2018-04-03 | 2018-08-31 | 湘潭大学 | The preparation method of 2,4- dichlorphenoxyacetic acids |
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