CN101434545A - Method for preparing methyl p-chloromethyl benzoate - Google Patents
Method for preparing methyl p-chloromethyl benzoate Download PDFInfo
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- CN101434545A CN101434545A CNA2008102368760A CN200810236876A CN101434545A CN 101434545 A CN101434545 A CN 101434545A CN A2008102368760 A CNA2008102368760 A CN A2008102368760A CN 200810236876 A CN200810236876 A CN 200810236876A CN 101434545 A CN101434545 A CN 101434545A
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Abstract
The invention discloses a preparation method of parachloro-methyl benzoate, which mainly adopts methyl p-methyl benzoate obtained from the esterification reaction between methyl p-formic acid and methanol as a raw material, and introduces chlorine gas under the action of a catalyst so as to lead side chains to be subjected to a chloride reaction, and then carries out distillation for recovering unreacted raw materials so as to finally obtain an end product. The technology has simple operation process, stability, high yield, low cost and applicability to industrialized production.
Description
Technical field
The present invention relates to the manufacture method of Chemicals, particularly a kind of preparation is to the method for chloromethyl benzoic acid methyl esters.
Background technology
To the chloromethyl benzoic acid methyl esters is a kind of important organic fine chemical and intermediate, and it can be used for aspects such as synthetic medicine and agricultural chemicals.
To the disclosed documents and materials of the preparation of chloromethyl benzoic acid methyl esters few (we do not retrieve related data temporarily).If this target compound was divided into for two steps: be that raw material and methanol esterification obtain methyl p-methyl benzoate with the p-methylbenzoic acid earlier, again methyl p-methyl benzoate can be obtained product by chlorination.The synthetic method of the first step methyl p-methyl benzoate is the esterification that belongs to classical, " practical Minute Organic Synthesis handbook (in January, 2000 first version that this well-known process is write at Duan Hangxin, the 126th～131 page) in discuss to some extent, in the present invention the first step esterification technique process is not discussed the chlorination of primary study ester.
The chlorination of methyl p-methyl benzoate mainly is to occur on its methyl group, it belongs to the side chain chlorination of aromatics, this type of compound research is in the past very many, this process is described in Tang Pei Kun chief editor " Minute Organic Synthesis chemistry and technology " (in January, 2002 first version, the 68th～85 page), ZL200610018249.0 to some extent.Its chemical reaction of side chain chloro is a kind of free radical lock reaction, need carry out under light or chemical catalyst initiation.
In above-mentioned technological process, be raw material with aromatic alkyl hydrocarbon and chlorine, under the catalysis of light or chemical catalyst such as Diisopropyl azodicarboxylate, under 80 ℃-150 ℃ of temperature, react; Stopped reaction when the chlorination transformation efficiency of former material is 30%-70% (mass ratio, down together) carries out rectification under vacuum with reaction product and can get product.Unreacted raw material and middle runnings recycling, the HCl gas that reaction produces are absorbed to handle by the absorption tower makes technical hydrochloric acid.
Summary of the invention
The object of the present invention is to provide a kind of easy and simple to handle, yield is high, production cost is low, be easy to the manufacture method to the chloromethyl benzoic acid methyl esters of suitability for industrialized production.
Technical scheme of the present invention is:
The methyl-toluate that is obtained by p-methylbenzoic acid and methyl alcohol generation esterification is in advance placed reaction vessel, under the catalysis of UV-light or Diisopropyl azodicarboxylate, feeding chlorine makes side chain carry out chlorination, reclaim unreacted methyl p-methyl benzoate through rectifying again and can obtain finished product, the processing condition of reaction are: the chlorination transformation efficiency is 20%-70% (mass ratio), temperature of reaction is 70 ℃-140 ℃, and speed of reaction is 6%-15%/h (mass ratio).
Chlorination transformation efficiency preferred value in the above-mentioned processing condition is 30%-35%.
Temperature of reaction preferred value in the above-mentioned processing condition is 100 ℃-110 ℃.
Target product of the present invention-can be divided into two operational paths: 1. first esterification post chlorization, esterification after the 2. first chlorination to the synthetic route of chloromethyl benzoic acid methyl esters.Though the reaction method of two lines all can obtain product, but carrying out the intermediate that chlorination reaction obtains-to chloromethyl benzoic acid in the second operational path earlier is solids, its refining purification is difficulty, because of its boiling point height, can not make with extra care with rectification method, reach refining purification so must use solvent such as chlorobenzene to carry out recrystallization.Thus, production cost height not only, and increased contaminate environment.By contrast, intermediate-methyl p toluate that first esterification obtains in article one operational path is a liquids, and its refining purification is then much easier, and its boiling point is low, and available rectification method is made with extra care purification.Based on the above, so method for selecting of the present invention is the operational path of first esterification post chlorization, its reaction formula is as follows:
Main reaction:
The paratolunitrile methyl p toluate
To the chloromethyl benzoic acid methyl esters
Side reaction
P-methylbenzoic acid and methyl alcohol generation esterification obtain the intermediate methyl p-methyl benzoate through rectifying, its content 99% (GC, area %, down together) more than.Methyl p-methyl benzoate feeds chlorine and makes side chain generation chlorination under ultraviolet lighting, obtain chloromethyl benzoic acid methyl esters crude product, reclaims unreacted methyl p-methyl benzoate and obtains the product finished product through rectifying again, and its content can reach more than 98% (GC).
In production process of the present invention, the transformation efficiency of control chlorination is of paramount importance, secondly is temperature of reaction.Can find the chlorination of methyl p-methyl benzoate phenyl ring that from the following table data after chloromethyl benzoic acid methyl esters content was surpassed 30% (GC), the height impurity that boils obviously increased.In order to improve the selectivity of reaction, suitably reduce the transformation efficiency of one way chloro, can significantly reduce the generation of by product, it is preferable that the per pass conversion of chloro is controlled at 30%-35%.
Methyl p-methyl benzoate chlorination change of component data statistic
Simultaneously, the component of product distributes relevant with temperature of reaction in the chlorination.In the time of 70 ℃-140 ℃, chlorination can normally carry out, and when raising more than 140 ℃ along with temperature, the height impurity that boils increases sharply; On behalf of the master, side reaction is then based on substitution reaction on the phenyl ring during low temperature with methyl dichloro in side reaction during high temperature.
Technology of the present invention is easy, and is easy to operate, the product yield height, and production cost is low, is suitable for suitability for industrialized production.
Embodiment
The present invention can be in conjunction with furthermore bright its technological process of following embodiment, and embodiment is usefulness as an illustration only, and unrestricted protection scope of the present invention.
Embodiment 1
In the exsiccant there-necked flask, add the synthetic in advance good methyl p-methyl benzoate (content: 99.52% of 600g, GC), connect the hydrogen chloride absorption device, open high voltage mercury lamp and intensification, when reaching 100 ℃, regulate certain speed and import chlorine to the reaction flask bottom, temperature of reaction is controlled at 100 ℃-110 ℃, and the reaction times is 4 hours, and timing sampling detects; After reaction finishes nitrogen fed in the product removing residual hydrogenchloride, product 652g.Gas chromatographic analysis methyl p-methyl benzoate content is 57.16%, and parachlorotoluene methyl-formiate content is 35.25%, and the foreign matter content that gently boils is 2.82%, and other height content that boils is 4%.
Embodiment 2
Add the methyl p-methyl benzoate of 900g in the exsiccant there-necked flask, transfer and be twice the chlorine import volume, other operational condition is with example 1, and the reaction times is 2 hours; After finishing, reaction gets product 1013g.Gas chromatographic analysis methyl p-methyl benzoate content is 45.93%, is 42.75% to chloromethyl benzoic acid methyl esters content, and the foreign matter content that gently boils is 3.53%, and other height content that boils is 7.39%.
Embodiment 3
The product of embodiment 2 gained is carried out rectification under vacuum (about 8 of rectifying column stage number), N
2Protection; 160 ℃ of-165 ℃/300mmHg cuts are collected in control reflux ratio 1:1～3, get finished product to chloromethyl benzoic acid methyl esters 335.7g, content 98.32% (GC), once through yield 58.33%.The low cut 440g that boils of rectifying, main component is that (content 99.79% GC), can repeat logical chlorine to methyl p-methyl benzoate; Rectifying interim fraction 120.3g contains product 64.19% (GC); Tankage 111g contains product 21.34% (GC).
Claims (3)
1. manufacture method to the chloromethyl benzoic acid methyl esters, it is characterized in that: the tolyl acid that will be obtained by p-methylbenzoic acid and methyl alcohol generation esterification in advance places reaction vessel, under the catalysis of UV-light or Diisopropyl azodicarboxylate, feeding chlorine makes side chain carry out chlorination, reclaim through rectifying again and unreactedly can obtain finished product the methylbenzene methyl esters, the processing condition of reaction are: the chlorination transformation efficiency is 20%-70% (mass ratio), temperature of reaction is 70 ℃-140 ℃, speed of reaction 6%-15%/h (mass ratio).
2. by the described manufacture method to the chloromethyl benzoic acid methyl esters of claim 1, it is characterized in that: the chlorination transformation efficiency preferred value in the above-mentioned processing condition is 30%-35%.
3. by the described manufacture method to the chloromethyl benzoic acid methyl esters of claim 1, it is characterized in that: the temperature of reaction preferred value in the above-mentioned processing condition is 100 ℃-110 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CNA2008102368760A CN101434545A (en) | 2008-12-17 | 2008-12-17 | Method for preparing methyl p-chloromethyl benzoate |
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| CNA2008102368760A CN101434545A (en) | 2008-12-17 | 2008-12-17 | Method for preparing methyl p-chloromethyl benzoate |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503355A (en) * | 2019-01-03 | 2019-03-22 | 唐更好 | A kind of preparation method of p-chloromethyl benzoic acid |
| CN111606829A (en) * | 2020-07-07 | 2020-09-01 | 淄博腾煜化工工程有限公司 | Production method of o-methyl formate benzyl sulfonamide |
| CN114805120A (en) * | 2022-05-23 | 2022-07-29 | 江苏瑞达环保科技有限公司 | Synthesis process of m-cyanomethyl benzoate |
-
2008
- 2008-12-17 CN CNA2008102368760A patent/CN101434545A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503355A (en) * | 2019-01-03 | 2019-03-22 | 唐更好 | A kind of preparation method of p-chloromethyl benzoic acid |
| CN111606829A (en) * | 2020-07-07 | 2020-09-01 | 淄博腾煜化工工程有限公司 | Production method of o-methyl formate benzyl sulfonamide |
| CN114805120A (en) * | 2022-05-23 | 2022-07-29 | 江苏瑞达环保科技有限公司 | Synthesis process of m-cyanomethyl benzoate |
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Open date: 20090520 |