CN102775308A - Method for preparing ethyl 2-(4-hydroxyphenoxy) propinoate - Google Patents
Method for preparing ethyl 2-(4-hydroxyphenoxy) propinoate Download PDFInfo
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- CN102775308A CN102775308A CN2012102218172A CN201210221817A CN102775308A CN 102775308 A CN102775308 A CN 102775308A CN 2012102218172 A CN2012102218172 A CN 2012102218172A CN 201210221817 A CN201210221817 A CN 201210221817A CN 102775308 A CN102775308 A CN 102775308A
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- Prior art keywords
- hydroxyphenoxy
- ethanol
- reaction kettle
- propionic acid
- weight parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 238000000034 method Methods 0.000 title abstract description 12
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- AQIHDXGKQHFBNW-UHFFFAOYSA-N 2-(4-hydroxyphenoxy)propanoic acid Chemical compound OC(=O)C(C)OC1=CC=C(O)C=C1 AQIHDXGKQHFBNW-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000005886 esterification reaction Methods 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- FKRCODPIKNYEAC-UHFFFAOYSA-N propionic acid ethyl ester Natural products CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 19
- -1 2-(4-hydroxyphenoxy) ethyl Chemical group 0.000 claims description 18
- 230000032050 esterification Effects 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- ILYSHPJWNMPBPE-UHFFFAOYSA-N ethyl 2-(4-hydroxyphenoxy)propanoate Chemical compound CCOC(=O)C(C)OC1=CC=C(O)C=C1 ILYSHPJWNMPBPE-UHFFFAOYSA-N 0.000 abstract 3
- 238000005119 centrifugation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 3
- YXHKONLOYHBTNS-UHFFFAOYSA-N Diazomethane Chemical compound C=[N+]=[N-] YXHKONLOYHBTNS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 2
- SXERGJJQSKIUIC-UHFFFAOYSA-N 2-Phenoxypropionic acid Chemical class OC(=O)C(C)OC1=CC=CC=C1 SXERGJJQSKIUIC-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- OSUHJPCHFDQAIT-UHFFFAOYSA-N ethyl 2-{4-[(6-chloroquinoxalin-2-yl)oxy]phenoxy}propanoate Chemical group C1=CC(OC(C)C(=O)OCC)=CC=C1OC1=CN=C(C=C(Cl)C=C2)C2=N1 OSUHJPCHFDQAIT-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- BACHBFVBHLGWSL-UHFFFAOYSA-N methyl 2-[4-(2,4-dichlorophenoxy)phenoxy]propanoate Chemical group C1=CC(OC(C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-UHFFFAOYSA-N 0.000 description 1
- 230000009965 odorless effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical class O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- BACHBFVBHLGWSL-JTQLQIEISA-N rac-diclofop methyl Natural products C1=CC(O[C@@H](C)C(=O)OC)=CC=C1OC1=CC=C(Cl)C=C1Cl BACHBFVBHLGWSL-JTQLQIEISA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for preparing the ethyl 2-(4-hydroxyphenoxy) propionate. The method includes adding, by weight, 261.5 parts of 2-(4-Hydroxyphenoxy) propionic acid and 3.4 parts of toluene into a reaction kettle wholly for one time, adding, by weight, 86 parts of ethanol in batches, keeping the reaction kettle at a constant pressure and at a temperature of 70 DEG C after adding a first batch of the ethanol, measuring material components in the reaction kettle, and reducing the pressure and distill the mixture after a reaction end point is reached to separate moisture produced by an esterification reaction; measuring material components in the reaction kettle, if the 2-(4-Hydroxyphenoxy) propionic acid exists, adding the ethanol continuously to perform reaction, the reaction is performed until the 86 parts of ethanol is completely added; reducing the temperature to the room temperature; adding water to wash the mixture, reducing temperature and distilling the mixture, absorbing impurities, cooling the mixture to crystallize, and performing centrifugation and drying to obtain the ethyl 2-(4-hydroxyphenoxy) propionate. The method for preparing the ethyl 2-(4-hydroxyphenoxy) propionate has the advantages of being simple to operate, low in cost, small in pollution, and suitable for industrial large scale application.
Description
Technical field
The present invention relates to a kind of preparation method of herbicide intermediate, specifically relate to the preparation method of a kind of 2-(4-hydroxyphenoxy) ethyl propionate.
Background technology
2-(4-hydroxyphenoxy) ethyl propionate, molecular formula is HOC
6H
4OCH (CH
3) COOC
2H
5, be the Sandy oily liquids, odorless, tasteless.It is crucial middle the stopping of phenoxy propionic acid class weedicide such as quizalofopethyl, diclofop-methyl etc., and this type highy potent herbicide can selectively be prevented and kill off 1 year or perennial gramineous weeds, and consumption is few, and the person poultry harmless is so used by various countries at present widely.
This midbody compound synthetic difficulty is: one, Resorcinol oxidation by air easily in basic soln; Two, nucleophilic substitution can take place in two of Resorcinol phenolic hydroxyl groups simultaneously; Three, alpha-chloro propionic acid α-chlorine in basic soln is prone to by OH
-Replace.At present, in the existing method of synthetic this midbody compound, relatively be typically: (1) as solvent, makes the condensation under alkaline medium calcium hydroxide of alpha-brominated propionic ester and Resorcinol with methyl-sulphoxide at low temperatures; (2) use nitrogen protection, make alpha-chloro propionic acid and Resorcinol condensation, use the diazomethane esterification, obtain product through transesterification reaction again.
The shortcoming of method (1) has been to use expensive methyl-sulphoxide and alpha-brominated propionic acid, although nucleophilic substitution takes place alpha-brominated thing easily, has also increased the disubstituted trend of Resorcinol; For preventing disubstituted generation, need with excessive Resorcinol, be 2.5:1 such as the mol ratio of Resorcinol and alpha-chloro propionic acid; So just cause a large amount of wastes of Resorcinol, the entire reaction time is about 40h, therefore; This method cost is high, and is consuming time many.
Method (2) needs to use nitrogen protection, and intermediate treatment is cumbersome, and has used severe toxicity and explosive diazomethane, and therefore, the extensive use of this method also is restricted.
Summary of the invention
Shortcoming and defect to the prior art existence; The invention provides a kind of employing 2-(4-hydroxyphenoxy) propionic acid and ethanol is the method that main raw material prepares 2-(4-hydroxyphenoxy) ethyl propionate, and the present invention is simple to operate, and cost is low; Pollute and lack, be suitable for industry and go up large-scale application.
The present invention realizes through following technical scheme:
The preparation method of a kind of 2-(4-hydroxyphenoxy) ethyl propionate may further comprise the steps:
Get the raw materials ready according to 2-(4-hydroxyphenoxy) propionic acid of 261.5 weight parts, the toluene of 3.4 weight parts and the ethanol of 86 weight parts;
Once all add in the reaction kettle 2-(4-hydroxyphenoxy) propionic acid of said 261.5 weight parts and the toluene of said 3.4 weight parts; The ethanol of said 86 weight parts adds in batches; After first batch of ethanol adds; 70 ℃ of insulations of said reaction kettle normal pressure vacuumize and carry out underpressure distillation, to isolate the moisture that esterification produces; Measure the material composition in the said reaction kettle; Confirm the concentration of 2-(4-hydroxyphenoxy) propionic acid; And then in said reaction kettle, add second batch of ethanol; Make remaining 2-in ethanol and the said reaction kettle (4-hydroxyphenoxy) propionic acid accomplish esterification and generate 2-(4-hydroxyphenoxy) ethyl propionate, continue then to vacuumize and carry out underpressure distillation, the moisture that esterification produces in the material is steamed through distillation; Measure the material composition in the said reaction kettle once more,, then continue to add ethanol and carry out esterification if still have 2-(4-hydroxyphenoxy) propionic acid to exist, so repeatedly, till the ethanol of said 86 weight parts adds fully;
The temperature of said reaction kettle is reduced to room temperature;
Add water washing, underpressure distillation, adsorption-edulcoration, crystallisation by cooling, centrifugal, dry, promptly get 2-(4-hydroxyphenoxy) ethyl propionate.
Preferably, said first batch of alcoholic acid add-on is 2/3 of an ethanol total amount.
Preferably, purity >=99% of said 2-(4-hydroxyphenoxy) propionic acid, said alcoholic acid purity >=99%, the purity of said toluene >=99%.
2-(4-hydroxyphenoxy) propionic acid and alcoholic acid esterification generate the reaction equation of 2-(4-hydroxyphenoxy) ethyl propionate shown in formula I.
It is the method that main raw material prepares 2-(4-hydroxyphenoxy) ethyl propionate that
the present invention adopts 2-(4-hydroxyphenoxy) propionic acid and ethanol, have simple to operate, cost is low, pollute less, be suitable for the beneficial effect that large-scale application is gone up in industry.
Description of drawings
Fig. 1 is the process flow sheet of preparation 2-(4-hydroxyphenoxy) ethyl propionate.
Embodiment
In order to further specify technical scheme of the present invention; Below in conjunction with embodiment the preferred embodiment of the invention is described; Describe just in order to further specify feature and advantage of the present invention but should be appreciated that these, rather than to the restriction of claim of the present invention.
The purity of 2-(4-hydroxyphenoxy) propionic acid, ethanol and toluene that present embodiment is used all >=99%.
The preparation method of a kind of 2-(4-hydroxyphenoxy) ethyl propionate may further comprise the steps (as shown in Figure 1):
Get the raw materials ready according to 2-(4-hydroxyphenoxy) propionic acid of 261.5kg, the toluene of 3.4kg and the ethanol of 86kg;
Once all add in the reaction kettle 2-(4-hydroxyphenoxy) propionic acid of 261.5kg and the toluene of 3.4kg; The ethanol of 86kg adds in batches; The first batch of ethanol 57kg (account for ethanol total amount 2/3) that adds, after adding, 70 ℃ of insulations of reaction kettle normal pressure 1h; Vacuumize and carry out underpressure distillation, to isolate moisture and a small amount of unreacted ethanol that esterification produces; And then in reaction kettle, add second crowd of ethanol 17kg; Make remaining 2-in ethanol and the reaction kettle (4-hydroxyphenoxy) propionic acid accomplish esterification basically and generate 2-(4-hydroxyphenoxy) ethyl propionate; Continue then to vacuumize and carry out underpressure distillation, the moisture that unreacted ethanol and esterification produce in the material is steamed through distillation; Material composition in the assaying reaction still if still have 2-(4-hydroxyphenoxy) propionic acid to exist, then continues to add ethanol and reacts once more, so repeatedly, and till the ethanol of 86kg adds fully;
The temperature of reaction kettle is reduced to room temperature;
Add water washing, underpressure distillation, adsorption-edulcoration, crystallisation by cooling, centrifugal, dry, promptly get 2-(4-hydroxyphenoxy) ethyl propionate.
Claims (3)
1. the preparation method of a 2-(4-hydroxyphenoxy) ethyl propionate is characterized in that said preparation method may further comprise the steps:
Get the raw materials ready according to 2-(4-hydroxyphenoxy) propionic acid of 261.5 weight parts, the toluene of 3.4 weight parts and the ethanol of 86 weight parts;
Once all add in the reaction kettle 2-(4-hydroxyphenoxy) propionic acid of said 261.5 weight parts and the toluene of said 3.4 weight parts; The ethanol of said 86 weight parts adds in batches; After first batch of ethanol adds; 70 ℃ of insulations of said reaction kettle normal pressure vacuumize and carry out underpressure distillation, to isolate the moisture that esterification produces; Measure the material composition in the said reaction kettle; Confirm the concentration of 2-(4-hydroxyphenoxy) propionic acid; And then in said reaction kettle, add second batch of ethanol; Make remaining 2-in ethanol and the said reaction kettle (4-hydroxyphenoxy) propionic acid accomplish esterification and generate 2-(4-hydroxyphenoxy) ethyl propionate, continue then to vacuumize and carry out underpressure distillation, the moisture that esterification produces in the material is steamed through distillation; Measure the material composition in the said reaction kettle once more,, then continue to add ethanol and carry out esterification if still have 2-(4-hydroxyphenoxy) propionic acid to exist, so repeatedly, till the ethanol of said 86 weight parts adds fully;
The temperature of said reaction kettle is reduced to room temperature;
Add water washing, underpressure distillation, adsorption-edulcoration, crystallisation by cooling, centrifugal, dry, promptly get 2-(4-hydroxyphenoxy) ethyl propionate.
2. the preparation method of 2-according to claim 1 (4-hydroxyphenoxy) ethyl propionate is characterized in that said first batch of alcoholic acid add-on is 2/3 of an ethanol total amount.
3. the preparation method of 2-according to claim 1 and 2 (4-hydroxyphenoxy) ethyl propionate is characterized in that, purity >=99% of said 2-(4-hydroxyphenoxy) propionic acid, said alcoholic acid purity >=99%, the purity of said toluene >=99%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102218172A CN102775308A (en) | 2012-07-01 | 2012-07-01 | Method for preparing ethyl 2-(4-hydroxyphenoxy) propinoate |
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|---|---|---|---|
| CN2012102218172A CN102775308A (en) | 2012-07-01 | 2012-07-01 | Method for preparing ethyl 2-(4-hydroxyphenoxy) propinoate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928131A (en) * | 2017-01-20 | 2017-07-07 | 江苏凯晨化工有限公司 | A kind of preparation method of haloxyfop-r-methyl |
-
2012
- 2012-07-01 CN CN2012102218172A patent/CN102775308A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106928131A (en) * | 2017-01-20 | 2017-07-07 | 江苏凯晨化工有限公司 | A kind of preparation method of haloxyfop-r-methyl |
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| PB01 | Publication | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121114 |