CN1757628A - Method for preparing 2-(P-chloromethyl phenyl) propionic acid/ester - Google Patents
Method for preparing 2-(P-chloromethyl phenyl) propionic acid/ester Download PDFInfo
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- CN1757628A CN1757628A CN 200510119813 CN200510119813A CN1757628A CN 1757628 A CN1757628 A CN 1757628A CN 200510119813 CN200510119813 CN 200510119813 CN 200510119813 A CN200510119813 A CN 200510119813A CN 1757628 A CN1757628 A CN 1757628A
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- propionic acid
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Abstract
This invention discloses a reaction thermal balance regulation method in acetic acid production process through carbonyl synthesis with methanol under low pressure and liquid phase. In the production process of acetic acid synthesized with methanol and carbon monoxide, recirculating flash distillation mother liquor which has lower temperature than reaction temperature with a recirculating mother liquor pump to balance the thermal quantity of synthesis reactor, it is characterized by setting a heat exchanger after recirculating mother liquor pump, to decrease the temperature of mother liquor from 124 DEG C - 126 DEG C to 80 DEG C - 110 DEG C, to balance reaction heat of reaction system through decreasing the temperature of recirculating mother liquid. Compared with the heat exchange method through outside-recirculating of reactor, the invention avoids catalyst deposits in heat exchanger under high temperature because of insufficient carbon monoxide, and avoids corrosion of recirculating pump under high temperature medium as well.
Description
Technical field
The present invention relates to the method for a kind of Synthetic 2-(p-chloromethyl phenyl) propionic acid or ester II, especially relating to a kind of is raw material with 2-(p-aminomethyl phenyl) propionic acid (or ester) I, the method for Synthetic 2-(p-chloromethyl phenyl) propionic acid or ester II.
Background technology
The structural formula of 2-(p-chloromethyl phenyl) propionic acid/ester is:
Wherein, R=H or-CH3 or-CH2CH3.
2-(p-chloromethyl phenyl) propionic acid (or ester) is the important source material and the intermediate in agrochemistry, fine chemistry industry or pharmacy (for example anti-inflammatory anodyne etc.) field, and the synthetic chloromethylbenzene propionic acid of having reported at present and the method for derivative thereof have:
(1) patent No. provides the method for a kind of Synthetic 2-(p-chloromethyl phenyl) propionic acid (or ester) for the Japanese Patent of JP No.87-129250, promptly under the illumination effect, 2-(p-aminomethyl phenyl) propionic acid (or ester) and chlorine reaction generate 2-(p-chloromethyl phenyl) propionic acid (or ester).This method is had relatively high expectations to production unit and safety features because adopt chlorine.
(2) patent No. provides the method for a kind of Synthetic 2-(p-chloromethyl phenyl) propionic acid (or ester) for the United States Patent (USP) of US No:6013832, and its synthetic line is as follows:
Promptly use 2-phenylpropionic acid (or ester) III and hydroformylation reagent react to generate the methylolation product IV, reaction generates 2-(p-chloromethyl phenyl) propionic acid (or ester) V to IV with chlorinating agent more then.This method steps is more, and cost is higher.
Summary of the invention
The objective of the invention is to the shortcoming that exists in the method at existing Synthetic 2-(p-chloromethyl phenyl) propionic acid (or ester), providing a kind of is raw material with 2-(p-aminomethyl phenyl) propionic acid (or ester), with the SULPHURYL CHLORIDE is chlorination reagent, in the method for adding Synthetic 2-(p-chloromethyl phenyl) propionic acid (or ester) under radical initiator or the illumination condition.
Synthetic route of the present invention is as follows:
Wherein, R=H or-CH3 or-CH2CH3.
Step of the present invention is:
1) in reactor, adds raw material 2-(p-aminomethyl phenyl) propionic acid/ester and reaction solvent;
2) adding radical initiator, said radical initiator is 2,2 '-Diisopropyl azodicarboxylate (AIBN) or benzoyl peroxide (BPO), in reaction system, drip SULPHURYL CHLORIDE then; Or
Under illumination condition, in reaction system, drip SULPHURYL CHLORIDE then;
3) after reaction was finished, the cooling reaction solution filtered, and the gained solid obtains highly purified 2-(p-chloromethyl phenyl) propionic acid/ester with the mixed solvent recrystallization of benzene and sherwood oil.
In step 1), reaction solvent is selected from halogenated aryl hydrocarbon, aromatic hydrocarbons or tetracol phenixin, and said halogenated aryl hydrocarbon is selected from chlorobenzene, fluorobenzene, said aromatic hydrocarbons is selected from benzene.
In step 2) in, 68～73 ℃ of control temperature of reaction kettle slowly drip SULPHURYL CHLORIDE then in reaction system: or under illumination condition, 45～50 ℃ of control temperature of reaction kettle slowly drip SULPHURYL CHLORIDE then in reaction system.
The present invention is a raw material with 2-(p-aminomethyl phenyl) propionic acid (or ester), and the employing SULPHURYL CHLORIDE is a chlorination reagent, Synthetic 2-(p-chloromethyl phenyl) propionic acid (or ester).Compared with prior art, productive rate height of the present invention, low for equipment requirements, simple to operate, environmentally friendly, be the synthetic route of a suitable suitability for industrialized production.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
In being housed, the 250ml round-bottomed flask of mechanical stirrer and reflux condensing tube adds chlorobenzene 80g, 2-(p-aminomethyl phenyl) propionic acid 50g (0.305mol), 2,2 '-Diisopropyl azodicarboxylate (AIBN) 2.46g (0.015mol), control reaction temperature is 70 ℃ then, slowly drip SULPHURYL CHLORIDE 45.4g (0.336mol), add in the 3h.The reaction mixture cool to room temperature continues to be cooled to 0～5 ℃, suction filtration again, solid obtains 2-(p-chloromethyl phenyl) propionic acid 44.2g, productive rate 73% with the mixed solvent recrystallization of benzene and sherwood oil, product is a white crystal, and it is 98% that high pressure liquid chromatography detects its purity.1H?NMR(500M，CDCl3，ppm)：1.5(3H，d，J＝7.0Hz)，3.7(1H，q，J＝7.0Hz)，4.7(2H，s)，7.3(4H，dd)，11.3(1H，s，br)。IR(film)：3400，2950，1700，1420，1220cm-1。ESI-MS：m/z(％)＝199(100)[M+H]。
Embodiment 2
In being housed, the 250ml round-bottomed flask of mechanical stirrer and reflux condensing tube adds chlorobenzene 80g, 2-(p-aminomethyl phenyl) propionic acid 50g (0.305mol), under the mercury lamp irradiation, control reaction temperature is 48 ℃, slowly drip SULPHURYL CHLORIDE 45.4g (0.336mol), add in the 3h.The reaction mixture cool to room temperature continues to be cooled to 0～5 ℃ again, suction filtration, and solid obtains 2-(p-chloromethyl phenyl) propionic acid 43.0g, productive rate 71% with the mixed solvent recrystallization of benzene and sherwood oil.
Embodiment 3
In being housed, the 250ml round-bottomed flask of mechanical stirrer and reflux condensing tube adds benzene 80g, 2-(p-aminomethyl phenyl) propionic acid 50g (0.305mol), benzoyl peroxide (BPO) 3.63g (0.015mol), control reaction temperature is 75 ℃ then, slowly drip SULPHURYL CHLORIDE 45.4g (0.336mol), add in the 3h.The reaction mixture cool to room temperature continues to be cooled to 0～5 ℃, suction filtration again, solid obtains 2-(p-chloromethyl phenyl) propionic acid 42.4g, productive rate 70% with the mixed solvent recrystallization of benzene and sherwood oil, product is a white crystal, and it is 98% that high pressure liquid chromatography detects its purity.
Embodiment 4
With embodiment 1, just the solvent of reaction is changed into benzene, obtain 2-(p-chloromethyl phenyl) propionic acid 41.2g, productive rate 68%.
Embodiment 5
With embodiment 1, only the solvent of reaction is changed into fluorobenzene, obtain 2-(p-chloromethyl phenyl) propionic acid 42.4g, productive rate 70%.
Embodiment 6
Step just changes the solvent of reaction into tetracol phenixin with embodiment 1, obtains 2-(p-chloromethyl phenyl) propionic acid 33.9g, productive rate 56%.
Embodiment 7
In being housed, the 250ml round-bottomed flask of mechanical stirrer and reflux condensing tube adds chlorobenzene 80g, 2-(p-aminomethyl phenyl) methyl propionate 50g (0.284mol), 2,2 '-Diisopropyl azodicarboxylate (AIBN) 2.33g (0.0142mol), control reaction temperature is 70 ℃ then, slowly drip SULPHURYL CHLORIDE 42.1g (0.312mol), add in the 3h.The reaction mixture cool to room temperature continues to be cooled to 0～5 ℃ again, suction filtration, and solid obtains 2-(p-chloromethyl phenyl) methyl propionate 42.3g, productive rate 70% with the mixed solvent recrystallization of benzene and sherwood oil.
1H?NMR(500M，CDCl3，ppm)：1.5(3H，d，J＝7.0Hz)，3.65(3H，s)，3.7(1H，q，J＝7.0Hz)，4.7(2H，s)，7.3(4H，dd)，IR(film)：2950，1730，1430，1200，1160，1060cm-1，ESI-MS：m/z(％)＝213(100)[M+H]。
Claims (6)
1, the preparation method of 2-(p-chloromethyl phenyl) propionic acid/ester is characterized in that its synthetic route is as follows:
Wherein, R=H or-CH3 or-CH2CH3; Its synthesis step is:
1) in reactor, adds raw material 2-(p-aminomethyl phenyl) propionic acid/ester and reaction solvent;
2) adding radical initiator, said radical initiator is 2,2 '-Diisopropyl azodicarboxylate or benzoyl peroxide, in reaction system, drip SULPHURYL CHLORIDE then; Or
Under illumination condition, in reaction system, drip SULPHURYL CHLORIDE then;
3) after reaction was finished, the cooling reaction solution filtered, and the gained solid obtains highly purified 2-(p-chloromethyl phenyl) propionic acid/ester with the mixed solvent recrystallization of benzene and sherwood oil.
2, the preparation method of 2-as claimed in claim 1 (p-chloromethyl phenyl) propionic acid/ester is characterized in that in step 1), reaction solvent is selected from halogenated aryl hydrocarbon, aromatic hydrocarbons or tetracol phenixin.
3, the preparation method of 2-as claimed in claim 2 (p-chloromethyl phenyl) propionic acid/ester is characterized in that in step 1) said halogenated aryl hydrocarbon is selected from chlorobenzene, fluorobenzene.
4, the preparation method of 2-as claimed in claim 2 (p-chloromethyl phenyl) propionic acid/ester is characterized in that in step 1) said aromatic hydrocarbons is selected from benzene.
5, the preparation method of 2-as claimed in claim 1 (p-chloromethyl phenyl) propionic acid/ester is characterized in that in step 2) in, 68～73 ℃ of control temperature of reaction kettle drip SULPHURYL CHLORIDE then in reaction system.
6, the preparation method of 2-as claimed in claim 1 (p-chloromethyl phenyl) propionic acid/ester is characterized in that in step 2) in, under illumination condition, 45～50 ℃ of control temperature of reaction kettle drip SULPHURYL CHLORIDE then in reaction system.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510119813 CN1757628A (en) | 2005-11-07 | 2005-11-07 | Method for preparing 2-(P-chloromethyl phenyl) propionic acid/ester |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200510119813 CN1757628A (en) | 2005-11-07 | 2005-11-07 | Method for preparing 2-(P-chloromethyl phenyl) propionic acid/ester |
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| CN1757628A true CN1757628A (en) | 2006-04-12 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079711A (en) * | 2020-09-17 | 2020-12-15 | 白云山东泰商丘药业有限公司 | Preparation method of p-chloromethyl benzoic acid |
-
2005
- 2005-11-07 CN CN 200510119813 patent/CN1757628A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112079711A (en) * | 2020-09-17 | 2020-12-15 | 白云山东泰商丘药业有限公司 | Preparation method of p-chloromethyl benzoic acid |
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