CN104447288A - Method for preparing purified 2-methyl-4-chloropropionic acid - Google Patents

Method for preparing purified 2-methyl-4-chloropropionic acid Download PDF

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Publication number
CN104447288A
CN104447288A CN201410617246.3A CN201410617246A CN104447288A CN 104447288 A CN104447288 A CN 104447288A CN 201410617246 A CN201410617246 A CN 201410617246A CN 104447288 A CN104447288 A CN 104447288A
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reaction
mecopropp
present
chloropropionic acid
cresol
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孙国庆
侯永生
李宗清
朱小猛
黄效鹏
邱潇杨
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Shandong Weifang Rainbow Chemical Co Ltd
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Shandong Weifang Rainbow Chemical Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
    • C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
    • C07C51/367—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for preparing purified 2-methyl-4-chloropropionic acid. The method comprises the following steps: carrying out a first reaction on o-cresol and a first alkaline compound to obtain an o-cresol salt; carrying out a second reaction on S-2 chloropropionic acid and a second alkaline compound to obtain a chloropropionic acid salt; carrying out a third reaction on the o-cresol salt and the chloropropionic acid salt in methylbenzene to obtain o-toluene oxypropionate; and under the action of an alkaline compound, carrying out a fourth reaction on a pypocholoride and the o-toluene oxypropionate to obtain the purified 2-methyl-4-chloropropionic acid. The optical content of the purified 2-methyl-4-chloropropionic acid prepared by the method provided by the invention is higher. In addition, the optical loss of the method provided by the invention in a preparation process of the purified 2-methyl-4-chloropropionic acid is smaller; moreover, the method provided by the invention can be used for preventing the generation of dioxin, to ensure a higher yield of the purified 2-methyl-4-chloropropionic acid; and the method for preparing purified 2-methyl-4-chloropropionic acid provided by the invention is simple in process and smaller in environmental pollution.

Description

A kind of preparation method of mecopropP
Technical field
The present invention relates to compou nd synthesis technical field, particularly relate to a kind of preparation method of mecopropP.
Background technology
Vi par, referred to as MCPP, is a kind of Phenoxyacid herbicide, is mainly used in cereal crop except weeds such as lamb's-quarters, Tender Catchweed Bedstraw Herb and chickweeds.MCPP has chiral structure, usually the MCPP product prepared is raceme mixture, i.e. dextrorotation R-body and its enantiomer left-handed S-body mixture, but weeding activity structure almost all concentrates on R-body in MCPP, S-body does not almost have weeding activity, and S-body degradation rate is in the environment comparatively slow, the market outlook of therefore producing the Vi par of R-body are more wide.
The Vi par of R-body is otherwise known as mecopropP.At present, the preparation method of mecopropP is mainly, and splits 2 chloropropionic acids prepare S-2 chloropropionic acid by biological enzyme orientation; Ortho-cresol is adopted to prepare the methoxone phenol that purity is 99%; Under the condition of alcoholic solvent, S-2 chloropropionic acid and methoxone phenol are carried out condensation reaction, prepares mecopropP.Preparation method's technical maturity of this mecopropP that prior art provides, stable, but it is comparatively large to prepare optical loss in the process of mecopropP, makes the optics content of the mecopropP prepared lower, and needing to purify just can reach 95%.
Summary of the invention
In view of this, the object of the present invention is to provide a kind of preparation method of mecopropP, the optics content of the mecopropP that method provided by the invention prepares is higher.
The invention provides a kind of preparation method of mecopropP, comprising:
Ortho-cresol and the first basic cpd are carried out the first reaction, obtains ortho-cresol salt;
S-2 chloropropionic acid and the second basic cpd are carried out the second reaction, obtains chloropropionic acid salt;
Described adjacent formate and described chloropropionic acid salt are carried out the 3rd reaction in toluene, obtains adjacent first phenoxy propionic acid;
Under the effect of aminated compounds, hypochlorite and described adjacent first phenoxy propionic acid are carried out the 4th reaction, obtains mecopropP.
Preferably, the temperature of described first reaction is 110 DEG C ~ 150 DEG C.
Preferably, the temperature of described second reaction is 10 DEG C ~ 80 DEG C.
Preferably, the temperature of described 3rd reaction is 110 DEG C ~ 130 DEG C.
Preferably, the temperature of described 4th reaction is 0 DEG C ~ 60 DEG C.
Preferably, the time of described 4th reaction is 1 hour ~ 10 hours.
Preferably, the pH value of described 4th reaction is 7 ~ 12.
Preferably, described aminated compounds is one or more in dimethyl formamide, ethanamide and propionic acid amide.
Preferably, described first basic cpd and the second basic cpd are independently selected from alkali metal hydroxide.
Preferably, the described 3rd reacted after, the 3rd reaction product obtained is extracted, reclaim obtain ortho-cresol salt.
The invention provides a kind of preparation method of mecopropP, comprising: ortho-cresol and the first basic cpd are carried out the first reaction, obtains ortho-cresol salt; S-2 chloropropionic acid and the second basic cpd are carried out the second reaction, obtains chloropropionic acid salt; Described adjacent formate and described chloropropionic acid salt are carried out the 3rd reaction in toluene, obtains adjacent first phenoxy propionic acid; Under the effect of aminated compounds, hypochlorite and described adjacent first phenoxy propionic acid are carried out the 4th reaction, obtains mecopropP.Method provided by the invention adopts ortho-cresol and chloropropionic acid to prepare adjacent first phenoxy propionic acid in the basic conditions, then adopts hypochlorite to carry out chlorination the adjacent first phenoxy propionic acid obtained, and prepares mecopropP.The optics content of the mecopropP that this post chlorination processes provided by the invention prepares is higher, is beneficial to weeding application.Experimental result shows, optics content >=96% of the mecopropP that method provided by the invention prepares.
In addition, to prepare optical loss in the process of mecopropP less for method provided by the invention; Method provided by the invention can prevent the generation of dioxin, and the yield preparing mecopropP is higher; Preparation method's technique of mecopropP provided by the invention is simple, to the less pollution that environment produces.Experimental result shows, method provided by the invention prepares optical loss < 1.5% in the process of mecopropP; Purity >=97% of the mecopropP prepared, yield is in S-2 chloropropionic acid >=80%; In ortho-cresol >=90%.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only embodiments of the invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to the accompanying drawing provided.
Fig. 1 is the color atlas of the product that the embodiment of the present invention 1 prepares;
Fig. 2 is the optical purity color atlas of S-2 chloropropionic acid in the embodiment of the present invention 1;
Fig. 3 is the optical purity color atlas of the product that the embodiment of the present invention 1 prepares.
Embodiment
Be clearly and completely described the technical scheme in the embodiment of the present invention below, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
The invention provides a kind of preparation method of mecopropP, comprising:
Ortho-cresol and the first basic cpd are carried out the first reaction, obtains ortho-cresol salt;
S-2 chloropropionic acid and the second basic cpd are carried out the second reaction, obtains chloropropionic acid salt;
Described adjacent formate and described chloropropionic acid salt are carried out the 3rd reaction in toluene, obtains adjacent first phenoxy propionic acid;
Under the effect of aminated compounds, hypochlorite and described adjacent first phenoxy propionic acid are carried out the 4th reaction, obtains mecopropP.
Method provided by the invention adopts ortho-cresol and chloropropionic acid to prepare adjacent first phenoxy propionic acid in the basic conditions, then adopts hypochlorite to carry out chlorination the adjacent first phenoxy propionic acid obtained, and prepares mecopropP.The optics content of the mecopropP that this post chlorination processes provided by the invention prepares is higher.In addition, to prepare optical loss in the process of mecopropP less for method provided by the invention; Method provided by the invention can prevent the generation of dioxin, and the yield preparing mecopropP is higher; Preparation method's technique of mecopropP provided by the invention is simple, to the less pollution that environment produces.
Ortho-cresol and the first basic cpd are carried out the first reaction by the present invention, obtain ortho-cresol salt.In the present invention, the temperature of described first reaction is preferably 110 DEG C ~ 150 DEG C, is more preferably 115 DEG C ~ 140 DEG C, most preferably is 120 DEG C ~ 130 DEG C.In the present invention, the time of described first reaction is preferably 1 hour ~ 2 hours, is more preferably 1.2 hours ~ 1.8 hours, most preferably is 1.4 hours ~ 1.6 hours.
In the present invention, described first basic cpd is preferably alkali metal hydroxide, is more preferably sodium hydroxide or potassium hydroxide, most preferably is sodium hydroxide.In the present invention, described first basic cpd is preferably the first alkaline compound solution.In the present invention, the mass concentration of described first alkaline compound solution is preferably 30% ~ 50%, is more preferably 35% ~ 45%, most preferably is 40%.In the present invention, the mass ratio of described ortho-cresol and the first basic cpd is preferably 100:(10 ~ 110), be more preferably 100:(30 ~ 80), most preferably be 100:(40 ~ 60).
S-2 chloropropionic acid and the second basic cpd are carried out the second reaction by the present invention, obtain chloropropionic acid salt; Preferably the second basic cpd is joined in S-2 chloropropionic acid and carry out the second reaction, obtain chloropropionic acid salt.In the present invention, the temperature of described second reaction is preferably 10 DEG C ~ 80 DEG C, is more preferably 30 DEG C ~ 60 DEG C, most preferably is 40 DEG C ~ 50 DEG C.In the present invention, the time of described second reaction is preferably 1 hour ~ 2 hours, is more preferably 1.5 hours.
The source of the present invention to described S-2 chloropropionic acid does not have special restriction, can be bought obtain by market.In the present invention, described second basic cpd is preferably alkali metal hydroxide, is more preferably sodium hydroxide or potassium hydroxide, most preferably is sodium hydroxide.In the present invention, described second basic cpd is preferably the second alkaline compound solution.In the present invention, the mass concentration of described second alkaline compound solution is preferably 30% ~ 50%, is more preferably 35% ~ 45%, most preferably is 40%.In the present invention, the mass ratio of described S-2 chloropropionic acid and the second basic cpd is preferably 100:(10 ~ 110), be more preferably 100:(30 ~ 80), most preferably be 100:(40 ~ 60).
The time sequence of the present invention to described first reaction and the second reaction does not have special restriction, first can carry out the first reaction, first can carry out the second reaction yet, can also carry out the first reaction and the second reaction simultaneously.
After obtaining ortho-cresol salt and chloropropionic acid salt, described adjacent formate and described chloropropionic acid salt are carried out the 3rd reaction by the present invention in toluene, obtain adjacent first phenoxy propionic acid.The present invention preferably by toluene and described adjacent formate mixing, obtains mixture; In described mixture, add described chloropropionic acid salt carry out the 3rd reaction, obtain adjacent first phenoxy propionic acid.
In the present invention, the temperature of described 3rd reaction is preferably 110 DEG C ~ 130 DEG C, is more preferably 115 DEG C ~ 125 DEG C, most preferably is 120 DEG C.In the present invention, the time of described 3rd reaction is preferably 8 hours ~ 15 hours, is more preferably 10 hours ~ 12 hours.In the present invention, the mass ratio of described ortho-cresol salt and described chloropropionic acid salt is preferably (0.8 ~ 1.5): 1, is more preferably (1 ~ 1.2): 1.
Described 3rd reacted after, the present invention preferably extracts the 3rd reaction product obtained, reclaim obtain ortho-cresol salt.The present invention preferably reclaims ortho-cresol salt, and ortho-cresol salt recovery obtained, as reaction raw materials recycle, is prepared mecopropP, made the preparation method of mecopropP provided by the invention have good economy.
Toluene and described 3rd reaction product mixing preferably extract by the present invention, collect the oil phase after extraction;
3rd basic cpd and the mixing of described oil phase are carried out back extraction, obtains ortho-cresol salt.
Toluene and described 3rd reaction product mixing preferably extract by the present invention, collect the oil phase after extraction.In the present invention, the quality optimization of described toluene is 3 times ~ 7 times of described 3rd reaction product quality, is more preferably 4 times ~ 6 times, most preferably is 5 times.In the present invention, the temperature of described extraction is preferably 60 DEG C ~ 80 DEG C, is more preferably 70 DEG C ~ 80 DEG C, most preferably is 80 DEG C.Obtain more ortho-cresol salt to reclaim, the present invention preferably adopts toluene repeatedly to extract.The number of times of the present invention to described extraction does not have special restriction, and the number of times of described extraction preferably makes mass content≤0.1 of ortho-cresol in aqueous phase after extraction.The present invention does not have special restriction to the method detecting ortho-cresol mass content in the rear aqueous phase of extraction, adopts the method for detection o-cresol content well known to those skilled in the art, as available liquid phase marker method measures.In the present invention, the number of times of described extraction is preferably 2 times ~ 4 times, is more preferably 3 times.
Before extracting described 3rd reaction product, the present invention preferably carries out isothermal holding to described 3rd reaction product.In the present invention, the temperature of described isothermal holding is preferably 120 DEG C ~ 150 DEG C, is more preferably 130 DEG C ~ 140 DEG C.In the present invention, the time of described isothermal holding is preferably 0.5 hour ~ 1.5 hours, is more preferably 1 hour.
Before extracting described 3rd reaction product, the present invention preferably regulates pH value to 5 ~ 9 of described 3rd reaction product.In the present invention, the pH value of described 3rd reaction product is more preferably 6 ~ 8.The present invention preferably by the first acidic cpd and described 3rd reaction product mixing, regulates pH value to 5 ~ 9 of described 3rd reaction product.In the present invention, described first acidic cpd is preferably hydrochloric acid.In the present invention, described first acidic cpd is preferably the first acidic cpd solution.In the present invention, the mass concentration of described first acidic cpd solution is preferably 30% ~ 37%, is more preferably 32% ~ 35%.In the present invention, the mass ratio of described 3rd reaction product and the first acidic cpd is preferably 100:(10 ~ 110), be more preferably 100:(30 ~ 90), most preferably be 100:(50 ~ 70).
Before extracting described 3rd reaction product, described 3rd reaction product is preferably diluted by the present invention, obtains the material that mass concentration is 5% ~ 15%.In the present invention, the reagent of described dilution is preferably water.In the present invention, the mass concentration of described material is more preferably 8% ~ 12%, most preferably is 10%.
After collecting the oil phase after extraction, the 3rd basic cpd and the mixing of described oil phase are preferably carried out back extraction by the present invention, obtain ortho-cresol salt.In the present invention, described 3rd basic cpd is preferably alkali metal hydroxide, is more preferably sodium hydroxide or potassium hydroxide, most preferably is sodium hydroxide.In the present invention, described 3rd basic cpd is preferably the 3rd alkaline compound solution.In the present invention, the mass concentration of described 3rd alkaline compound solution is preferably 30% ~ 50%, is more preferably 35% ~ 45%, most preferably is 40%.
After obtaining adjacent first phenoxy propionic acid, hypochlorite and described adjacent first phenoxy propionic acid, under the effect of aminated compounds, are carried out the 4th reaction, obtain mecopropP by the present invention.In the present invention, the temperature of described 4th reaction is preferably 0 DEG C ~ 60 DEG C, is more preferably 5 DEG C ~ 50 DEG C, most preferably is 10 DEG C ~ 30 DEG C.In the present invention, the time of described 4th reaction is preferably 1 hour ~ 10 hours, is more preferably 3 hours ~ 8 hours, most preferably is 4 hours ~ 6 hours.
In the present invention, the pH value of described 4th reaction is preferably 7 ~ 12, is more preferably 8 ~ 11.The present invention preferably adopts basic cpd to regulate the pH value of described 4th reaction.The present invention preferably by the 4th basic cpd and described adjacent first phenoxy propionic acid mixing, obtains the first mixture; In described first mixture, add aminated compounds, obtain the second mixture; In described second mixture, add the second acidic cpd, obtain the 3rd mixture; In described 3rd mixture, add hypochlorite carry out the 4th reaction, obtain mecopropP.
The present invention preferably by the 4th basic cpd and described adjacent first phenoxy propionic acid mixing, obtains the first mixture.In the present invention, described 4th basic cpd is preferably alkali metal hydroxide, is more preferably sodium hydroxide or potassium hydroxide, most preferably is sodium hydroxide.In the present invention, described 4th basic cpd is preferably the 4th alkaline compound solution.In the present invention, the mass concentration of described 4th alkaline compound solution is preferably 30% ~ 50%, is more preferably 35% ~ 45%, most preferably is 40%.In the present invention, the consumption of described 4th basic cpd preferably makes the pH value of described first mixture be 7 ~ 9.
In the present invention, described second acidic cpd is preferably hydrochloric acid.In the present invention, described second acidic cpd is preferably the second acidic cpd solution.In the present invention, the mass concentration of described second acidic cpd solution is preferably 30% ~ 37%, is more preferably 32% ~ 35%.In the present invention, the consumption of described second acidic cpd preferably makes the pH value of the 3rd mixture be 7 ~ 9.
In the present invention, described aminated compounds is preferably one or more in dimethyl formamide, ethanamide and propionic acid amide, is more preferably dimethyl formamide.In the present invention, described hypochlorite is preferably clorox.In the present invention, the mass ratio of described aminated compounds and adjacent first phenoxy propionic acid is preferably 1:(7 ~ 10), be more preferably 1:(8 ~ 9).
The present invention preferably monitors the process of described 4th reaction, and when mass percent≤1% of adjacent first phenoxy propionic acid unreacted in described 4th reaction system, described 4th reaction terminates.In the present invention, the method for testing the mass percent of unreacted adjacent first phenoxy propionic acid in described 4th reaction system is preferably high performance liquid chromatography.
Described 4th reacted after, the present invention preferably by the obtain the 4th react product carry out acidifying, decrease temperature crystalline, filtration, drying, obtain mecopropP.In the present invention, the pH value of described acidifying preferably≤1.The present invention preferably adopts the 3rd acidic cpd to carry out described acidifying.In the present invention, described 3rd acidic cpd is preferably hydrochloric acid.In the present invention, the temperature of described acidifying is preferably 60 DEG C ~ 100 DEG C, is more preferably 70 DEG C ~ 90 DEG C, most preferably is 80 DEG C.In the present invention, the temperature of described decrease temperature crystalline is preferably 10 DEG C ~ 20 DEG C.In the present invention, the method for described filtration is preferably suction filtration.In the present invention, the temperature of described drying is preferably 50 DEG C ~ 80 DEG C, is more preferably 60 DEG C ~ 70 DEG C.In the present invention, the time of described drying is preferably 10 hours ~ 15 hours, is more preferably 12 hours.
Product method provided by the invention prepared carries out liquid chromatographic detection, and the condition of described liquid chromatographic detection is: the volumetric flask product that method provided by the invention for 0.05g prepares being placed in 25mL, uses moving phase constant volume; Chromatographic column is C18 post (150mm × 4.6mm × 0.5um); Moving phase is methyl alcohol, water and phosphoric acid, and the volume ratio of first alcohol and water is 65:35, with phosphoric acid, the pH value of the mixture of first alcohol and water is adjusted to 3.0; Determined wavelength is 229nm; Flow rate of mobile phase is 1.0ml/min; Sample size is 2uL.Detected result is, the color atlas appearance time of the product that method provided by the invention prepares is consistent with the appearance time of the reference colour spectrogram of mecopropP, it can thus be appreciated that the product that method provided by the invention prepares is mecopropP.
Liquid phase chromatography is adopted to detect the optics content of the mecopropP that method provided by the invention prepares, the testing conditions of liquid chromatography is: the volumetric flask mecopropP that the method provided by the invention of 0.05g prepares being placed in 25mL, adopts moving phase to carry out constant volume; Chromatographic column is lu × 5m lellulose-3; Moving phase is acetonitrile, water and trifluoroacetic acid, and the volume ratio of acetonitrile, water and trifluoroacetic acid is 20:80:0.1; Determined wavelength is 280nm; Flow rate of mobile phase is 1.0ml/min; Sample size is 10uL.The color atlas obtained during detecting optical content is designated as optical purity color atlas by the present invention, the optical purity color atlas that observation test obtains, the peak being 13.857min place by retention time in the optical purity color atlas obtained is designated as left-handed peak, is that the peak at 12.036min place is designated as dextrorotation peak by retention time; Calculating optical content by the following method:
Optics content=dextrorotation peak area/(left-handed peak area+dextrorotation peak area)
Detected result is, optics content >=96% of the mecopropP that method provided by the invention prepares.
Highly effective liquid phase chromatography detection method is adopted to carry out chromatogram detection to mecopropP provided by the invention and reference substance, described reference substance is the standard substance of mecopropP, according to detecting the color atlas of mecopropP provided by the invention and the color atlas of reference substance that obtain, adopt external standard method to do peak area ratio, calculate the chemical content of mecopropP provided by the invention; Concrete testing conditions is: chromatographic column is C18 post (150mm × 4.6mm × 0.5um); Moving phase is methyl alcohol, water and phosphoric acid, and the volume ratio of first alcohol and water is 65:35, with phosphoric acid, the pH value of the mixture of first alcohol and water is adjusted to 3.0; Determined wavelength is 229nm; Flow rate of mobile phase is 1.0ml/min; Sample size is 2uL.Repeatedly test under this testing conditions; The mass content of mecopropP in reference substance is designated as W 1, the average peak area of testing the reference substance color atlas obtained is designated as A 1, the average peak area that mecopropP the present invention prepared tests the color atlas obtained is designated as A, calculates the chemical content W of the mecopropP that the present invention prepares according to the following equation:
W＝A×W 1÷A 1
Test result is, chemical content >=97% of the mecopropP that method provided by the invention prepares.
In the present invention, described optical loss calculates according to the following equation:
Optical loss=E-F;
The optics content of E-S-2 chloropropionic acid;
F-mecopropP optics content.
The present invention adopts liquid phase chromatography to test the optics content of S-2 chloropropionic acid, the testing conditions of liquid chromatography is: the volumetric flask S-2 chloropropionic acid of 0.1g being placed in 25mL, the naphthylamines of 0.17g and the 2-oxyethyl group-1-oxyethyl group-1 of 0.24g is added in described volumetric flask, 2-dihydroquinoline (EEOQ), dissolve constant volume with methylene dichloride, at 30 DEG C, carry out the heating in water bath of 30 minutes; Chromatographic column is lu × 5m lellulose-1; Moving phase is normal hexane, methyl alcohol, ethanol and trifluoroacetic acid, and the volume ratio of normal hexane, methyl alcohol, ethanol and trifluoroacetic acid is 50:45:5:0.1; Determined wavelength is 224nm; Flow rate of mobile phase is 1.0ml/min; Sample size is 2uL.According to the method for calculation of the optics content described in technique scheme, the optics content calculating S-2 chloropropionic acid is 98.2%.Test result is, method provided by the invention prepares optical loss≤1.5% in mecopropP process.
MecopropP method provided by the invention prepared carries out liquid chromatographic detection, tests the purity of the mecopropP that method provided by the invention prepares; The condition of described liquid chromatographic detection is: the volumetric flask mecopropP that method provided by the invention for 0.05g prepares being placed in 25mL, uses moving phase constant volume; Chromatographic column is C18 post (150mm × 4.6mm × 0.5um); Moving phase is methyl alcohol, water and phosphoric acid, and the volume ratio of first alcohol and water is 65:35, with phosphoric acid, the pH value of the mixture of first alcohol and water is adjusted to 3.0; Determined wavelength is 229nm; Flow rate of mobile phase is 1.0ml/min; Sample size is 2uL.Detected result is, purity >=97% of the mecopropP that method provided by the invention prepares.
Calculate the yield that method provided by the invention prepares mecopropP according to the following equation:
Yield=C/D;
The mole number of C-actual mecopropP prepared;
The theoretical molar number of D-be converted into according to the raw material 100% the preparing mecopropP mecopropP of the preparation that mecopropP calculates.
Calculation result is, method provided by the invention prepares the yield of mecopropP in S-2 chloropropionic acid >=80%; In ortho-cresol >=90%.
The invention provides a kind of preparation method of mecopropP, comprising: ortho-cresol and the first basic cpd are carried out the first reaction, obtains ortho-cresol salt; S-2 chloropropionic acid and the second basic cpd are carried out the second reaction, obtains chloropropionic acid salt; Described adjacent formate and described chloropropionic acid salt are carried out the 3rd reaction in toluene, obtains adjacent first phenoxy propionic acid; Under the effect of aminated compounds, hypochlorite and described adjacent first phenoxy propionic acid are carried out the 4th reaction, obtains mecopropP.Method provided by the invention adopts ortho-cresol and chloropropionic acid to prepare adjacent first phenoxy propionic acid in the basic conditions, then adopts hypochlorite to carry out chlorination the adjacent first phenoxy propionic acid obtained, and prepares mecopropP.The optics content of the mecopropP that this post chlorination processes provided by the invention prepares is higher.In addition, to prepare optical loss in the process of mecopropP less for method provided by the invention; Method provided by the invention can prevent the generation of dioxin, and the yield preparing mecopropP is higher; Preparation method's technique of mecopropP provided by the invention is simple, to the less pollution that environment produces.
Raw material used in following examples of the present invention is commercial goods.
Embodiment 1
The mass concentration of the ortho-cresol and 82.5g that add 70.5g in the four-hole bottle of 250mL be 32.5% aqueous sodium hydroxide solution at 40 DEG C, carry out first reaction of 1 hour, obtain ortho-cresol sodium.
The mass concentration of the S-2 chloropropionic acid and 66.5g that add 60.03g in the four-hole bottle of 250mL is the second reaction that 32.5% aqueous sodium hydroxide solution carries out 2 hours at 30 DEG C, obtains chloropropionic acid sodium.
The toluene adding 765g in the above-mentioned ortho-cresol sodium of 153g carries out azeotropic dehydration, obtains dewatered product; In described dewatered product, dropwise add the above-mentioned chloropropionic acid sodium of 50.6g, then by temperature to 130 DEG C, the above-mentioned chloropropionic acid sodium continuing to drip 75.9g carries out the 3rd reaction of 10 hours.
Described 3rd reacted after, with 450g water, the 3rd reaction product obtained is diluted, obtains material; Described material is transferred to double glazing extraction kettle, be warming up to 80 DEG C, by dripping hydrochloric acid, the pH value of described material is adjusted to 5.5, the toluene adding 450g in described material extracts, detect the mass content of ortho-cresol in lower floor aqueous phase after extraction, repeat above-mentioned extraction process, until mass content≤0.1% of ortho-cresol in aqueous phase, by at every turn extraction after obtain oil phase mixing, obtain oil mixture.
The mass concentration adding 75g in described oil mixture be 10% aqueous sodium hydroxide solution mixing carry out back extraction, reclaim and obtain ortho-cresol sodium and the adjacent first phenoxy propionic acid of part, described ortho-cresol sodium can be used as reaction raw materials and prepares smart 2 first 4 chlorobenzene propionic acid.
After above-mentioned extraction completes, 30 DEG C are cooled to by extracting the aqueous phase obtained, in described aqueous phase, hydro-oxidation sodium regulates the pH value to 11 of described aqueous phase, obtain the first mixture, described first mixture is cooled to 25 DEG C, in described first mixture, add the dimethyl formamide of 10g, obtain the second mixture; In described second mixture, add hydrochloric acid regulate its pH value to 8, obtain the 3rd mixture; The clorox adding 596g in described 3rd mixture carries out the 4th reaction at 20 DEG C, hydrochloric acid is added in described 4th reaction process, the pH value controlling described 4th reaction is 6, terminate reaction when mass percent≤1% of adjacent first phenoxy propionic acid unreacted in described 4th reaction system, obtain the 4th reaction product;
After described 4th reaction product is warming up to 80 DEG C, adds hydrochloric acid and carry out acidifying, control pH value≤1 of described acidifying; The acidizing product obtained is cooled to 8 DEG C of crystallizations, suction filtration, dries 5 hours at 80 DEG C, obtain the product of 100.2g.
According to the method described in technique scheme, liquid chromatographic detection is carried out to the product that the embodiment of the present invention 1 obtains, detected result as shown in Figure 1, Fig. 1 is the color atlas of the product that the embodiment of the present invention 1 prepares, Fig. 1 is analyzed, analytical results is as shown in table 1, table 1 is Fig. 1 data results, and from Fig. 1 and table 1, the product that the embodiment of the present invention 1 prepares is mecopropP.
Table 1 Fig. 1 data results
Peak number Retention time Peak area Relative peak area (%) Remarks
1 0.673 10131 0.174
2 1.806 35327 0.606
3 5.916 13979 0.240
4 7.003 6897 0.118
5 8.152 8990 0.154
6 10.412 5756225 98.708 Product peak
Amount to 5831548 100.000
According to the method described in technique scheme, the chemical content of the mecopropP that the method that the test embodiment of the present invention 1 provides prepares, test result is, the chemical content of the mecopropP that the method that the embodiment of the present invention 1 provides prepares is 97.2%.
According to the method described in technique scheme, the method that the test embodiment of the present invention 1 provides prepares the optical loss in mecopropP process, Fig. 2 is the optical purity color atlas of S-2 chloropropionic acid in the embodiment of the present invention 1, Fig. 2 is analyzed, analytical results is as shown in table 2, and table 2 is Fig. 2 data results.
Table 2 Fig. 2 data results
Peak number Retention time Peak area Relative peak area (%) Remarks
1 5.216 209210 1.660 R-2 chloropropionic acid peak
2 5.758 374244 2.615 Solvent peak
3 8.392 13728963 95.725 S-2 chloropropionic acid peak
Amount to 14312416 100.000
Test result is, the method that the embodiment of the present invention 1 the provides optical loss prepared in mecopropP process is 0.9%.
According to the method described in technique scheme, the optics content of the mecopropP that the method that the test embodiment of the present invention 1 provides prepares, as shown in Figure 3, Fig. 3 is the optical purity color atlas of the product that the embodiment of the present invention 1 prepares to test result; Analyze Fig. 3, analytical results is as shown in table 3, and table 3 is Fig. 3 data results; From Fig. 3 and table 3, the optics content of the mecopropP that the method that the embodiment of the present invention 1 provides prepares is 97.4%.
Table 3 Fig. 3 data results
Peak number Retention time Peak area Relative peak area (%) Remarks
1 12.036 6376809 97.401 R-2 first 4 chloropropionic acid peak
2 13.857 132044 2.599 S-2 first 4 chloropropionic acid peak
Amount to 6508852 100.000
According to the method described in technique scheme, the purity of the mecopropP that the method that the test embodiment of the present invention 1 provides prepares, detected result is, purity >=97% of the mecopropP that the method that the embodiment of the present invention 1 provides prepares, yield counts 85.2% with S-2 chloropropionic acid, counts 95.6% with ortho-cresol.
Embodiment 2
The mass concentration of the ortho-cresol and 82.3g that add 70.4g in the four-hole bottle of 250mL be 32.5% aqueous sodium hydroxide solution at 40 DEG C, carry out first reaction of 1 hour, obtain ortho-cresol sodium.
The mass concentration of the S-2 chloropropionic acid and 66.5g that add 60.04g in the four-hole bottle of 250mL be 32.5% aqueous sodium hydroxide solution at 30 DEG C, carry out second reaction of 2 hours, obtain chloropropionic acid sodium.
The toluene adding 758g in the above-mentioned ortho-cresol sodium of 152.7g is warming up to 100 DEG C and dewaters, and obtains dewatered product; In described dewatered product, dropwise add the above-mentioned chloropropionic acid sodium of 43g, then by temperature to 128 DEG C, the above-mentioned chloropropionic acid sodium continuing to drip 83.5g carries out the 3rd reaction of 10 hours.
Described 3rd reacted after, the 3rd reaction product obtained is carried out the isothermal holding of 1h at 128 DEG C; With water, the 3rd reaction product after isothermal holding is diluted, obtain material; Described material is transferred to double glazing extraction kettle, be warming up to 80 DEG C, the pH value of described material is regulated to be 5.5 by dripping hydrochloric acid, the toluene adding 450g in described material extracts, detect the mass content of ortho-cresol in lower floor aqueous phase after extraction, repeat above-mentioned extraction process, until mass content≤0.1% of ortho-cresol in aqueous phase, by at every turn extraction after obtain oil phase mixing, obtain oil mixture.
By oil mixture obtained above and 75g mass concentration be 10% aqueous sodium hydroxide solution mixing carry out back extraction, reclaim obtain ortho-cresol sodium and the adjacent first phenoxy propionic acid of part, described ortho-cresol sodium can be used as reaction raw materials and prepares mecopropP.
After above-mentioned extraction completes, 30 DEG C are cooled to by extracting the aqueous phase obtained, in described aqueous phase, hydro-oxidation sodium regulates the pH value to 11 of described aqueous phase, obtain the first mixture, described first mixture is cooled to 25 DEG C, in described first mixture, adds the ethanamide of 8g, obtain the second mixture, in described second mixture, add hydrochloric acid regulate its pH value to 8, obtain the 3rd mixture; The clorox adding 596g in described 3rd mixture carries out the 4th reaction at 20 DEG C, hydrochloric acid is added in described 4th reaction process, the pH value controlling described 4th reaction is 6, terminate reaction when mass percent≤1% of adjacent first phenoxy propionic acid unreacted in described 4th reaction system, obtain the 4th reaction product;
After described 4th reaction product is warming up to 80 DEG C, adds hydrochloric acid and carry out acidifying, control pH value≤1 of described acidifying; Crystallization at the acidizing product obtained is cooled to 5 DEG C, suction filtration, 60 DEG C dry 5 hours, obtain the product of 98.2g.
Carry out liquid chromatographic detection according to the method described in technique scheme to the product that the embodiment of the present invention 2 obtains, detected result is, the product that the embodiment of the present invention 2 prepares is mecopropP.
According to the method described in technique scheme, the chemical content of the mecopropP that the method that the test embodiment of the present invention 2 provides prepares and optics content, test result is, the chemical content of the mecopropP that the method that the embodiment of the present invention 2 provides prepares is 97.5%, and optics content is 97.1%.
According to the method described in technique scheme, the method that the test embodiment of the present invention 2 provides prepares the optical loss in mecopropP process.Test result is, the method that the embodiment of the present invention 2 the provides optical loss prepared in mecopropP process is 1.1%.
According to the method described in technique scheme, the purity of the mecopropP that the method that the test embodiment of the present invention 2 provides prepares and yield, test result is, purity >=97% of the mecopropP that the method that the embodiment of the present invention 2 provides prepares, yield counts 83.2% with S-2 chloropropionic acid, counts 95.1% with ortho-cresol.
Embodiment 3
The mass concentration of the ortho-cresol and 82.5g that add 70.5g in the four-hole bottle of 250mL be 36.7% aqueous sodium hydroxide solution at 40 DEG C, carry out first reaction of 1 hour, obtain ortho-cresol sodium.
The mass concentration of the S-2 chloropropionic acid and 66.5g that add 60.03g in the four-hole bottle of 250mL be 36.7% aqueous sodium hydroxide solution at 30 DEG C, carry out second reaction of 2 hours, obtain chloropropionic acid sodium.
The toluene adding 765g in the above-mentioned ortho-cresol sodium of 153g is warming up to 100 DEG C and dewaters, and obtains dewatered product; In described dewatered product, dropwise add the above-mentioned chloropropionic acid sodium of 40.3g, then by temperature to 125 DEG C, the above-mentioned chloropropionic acid sodium continuing to drip 86.2g carries out the 3rd reaction of 10 hours.
Described 3rd reacted after, the 3rd reaction product obtained is carried out the isothermal holding of 1h at 125 DEG C; With 450g water, the 3rd reaction product after isothermal holding is diluted, obtain material; Described material is transferred to double glazing extraction kettle, be warming up to 80 DEG C, the pH value of described material is regulated to be 5.5 by dripping hydrochloric acid, the toluene adding 450g in described material extracts, detect the mass content of ortho-cresol in lower floor aqueous phase after extraction, repeat above-mentioned extraction process, until mass content≤0.1% of ortho-cresol in aqueous phase, by at every turn extraction after obtain oil phase mixing, obtain oil mixture.
By oil mixture obtained above and 75g mass concentration be 10% aqueous sodium hydroxide solution mixing carry out back extraction, reclaim obtain ortho-cresol sodium and the adjacent first phenoxy propionic acid of part, described ortho-cresol sodium can be used as reaction raw materials and prepares mecopropP.
After described extraction completes, be cooled to 30 DEG C by extracting the aqueous phase obtained, in described aqueous phase, hydro-oxidation sodium regulates the pH value to 11 of described aqueous phase, obtain the first mixture, described first mixture is cooled to 25 DEG C, in described first mixture, adds the propionic acid amide of 8g, obtain the second mixture; In described second mixture, add hydrochloric acid regulate its pH value to 8, obtain the 3rd mixture; The clorox adding 596g in described 3rd mixture carries out the 4th reaction at 20 DEG C, hydrochloric acid is added in described 4th reaction process, the pH value controlling described 4th reaction is 6, terminate reaction when mass percent≤1% of adjacent first phenoxy propionic acid unreacted in described 4th reaction system, obtain the 4th reaction product;
After described 4th reaction product is warming up to 80 DEG C, adds hydrochloric acid and carry out acidifying, control pH value≤1 of described acidifying; The acidizing product obtained is cooled to 7 DEG C of crystallizations, suction filtration, dries 5 hours at 70 DEG C, obtain the product of 95.8g.
Carry out liquid chromatographic detection according to the method described in technique scheme to the product that the embodiment of the present invention 3 obtains, detected result is, the product that the embodiment of the present invention 3 prepares is mecopropP.
According to the method described in technique scheme, the chemical content of the mecopropP that the method that the test embodiment of the present invention 3 provides prepares and optics content, test result is, the chemical content of the mecopropP that the method that the embodiment of the present invention 3 provides prepares is 97.2%, and optics content is 96.8%.
According to the method described in technique scheme, the method that the test embodiment of the present invention 3 provides prepares the optical loss in mecopropP process.Test result is, the method that the embodiment of the present invention 3 the provides optical loss prepared in mecopropP process is 1.5%.
According to the method described in technique scheme, the purity of the mecopropP that the method that the test embodiment of the present invention 3 provides prepares and yield, test result is, the purity of the mecopropP that the method that the embodiment of the present invention 3 provides prepares is 96.5%, yield counts 81.8% with S-2 chloropropionic acid, counts 91.3% with ortho-cresol.
Embodiment 4
The mass concentration of the ortho-cresol and 82.5g that add 70.5g in the four-hole bottle of 250mL be 36.7% aqueous sodium hydroxide solution at 40 DEG C, carry out first reaction of 1 hour, obtain ortho-cresol sodium.
The mass concentration of the S-2 chloropropionic acid and 66.5g that add 60.03g in the four-hole bottle of 250mL be 36.7% aqueous sodium hydroxide solution at 30 DEG C, carry out second reaction of 2 hours, obtain chloropropionic acid sodium.
The toluene adding 750g in the above-mentioned ortho-cresol sodium of 153g is warming up to 100 DEG C and dewaters, and obtains dewatered product; In described dewatered product, dropwise add the above-mentioned chloropropionic acid sodium of 30g, then by temperature to 120 DEG C, the above-mentioned chloropropionic acid sodium continuing to drip 96.5g carries out the 3rd reaction of 10 hours.
Described 3rd reacted after, the 3rd reaction product obtained is carried out the isothermal holding of 1h at 120 DEG C; With 450g water, the 3rd reaction product after isothermal holding is diluted, obtain material; Described material is transferred to double glazing extraction kettle, be warming up to 80 DEG C, the pH value of described material is regulated to be 5.5 by dripping hydrochloric acid, the toluene adding 450g in described material extracts, detect the mass content of ortho-cresol in lower floor aqueous phase after extraction, repeat above-mentioned extraction process, until mass content≤0.1% of ortho-cresol in aqueous phase, by at every turn extraction after obtain oil phase mixing, obtain oil mixture.
By oil mixture obtained above and 75g mass concentration be 10% aqueous sodium hydroxide solution mixing carry out back extraction, reclaim obtain ortho-cresol sodium and the adjacent first phenoxy propionic acid of part, described ortho-cresol sodium can be used as reaction raw materials and prepares mecopropP.
After described extraction completes, be cooled to 30 DEG C by extracting the aqueous phase obtained, in described aqueous phase, hydro-oxidation sodium regulates the pH value to 11 of described aqueous phase, obtains the first mixture; Described first mixture is cooled to 25 DEG C, in described first mixture, adds the dimethyl formamide of 8g, obtain the second mixture; In described second mixture, add hydrochloric acid regulate its pH value to 8, obtain the 3rd mixture; The clorox adding 596g in described 3rd mixture carries out the 4th reaction at 20 DEG C, hydrochloric acid is added in described 4th reaction process, the pH value controlling described 4th reaction is 6, terminate reaction when mass percent≤1% of adjacent first phenoxy propionic acid unreacted in described 4th reaction system, obtain the 4th reaction product;
After described 4th reaction product is warming up to 80 DEG C, adds hydrochloric acid and carry out acidifying, control pH value≤1 of described acidifying; The acidizing product obtained is cooled to 6 DEG C of crystallizations, suction filtration, dries 5 hours at 75 DEG C, obtain the product of 94.6g.
Carry out liquid chromatographic detection according to the method described in technique scheme to the product that the embodiment of the present invention 4 obtains, detected result is, the product that the embodiment of the present invention 4 prepares is mecopropP.
According to the method described in technique scheme, the chemical content of the mecopropP that the method that the test embodiment of the present invention 4 provides prepares and optics content, test result is, the chemical content of the mecopropP that the method that the embodiment of the present invention 4 provides prepares is 97.1%, and optics content is 96.5%.
According to the method described in technique scheme, the method that the test embodiment of the present invention 4 provides prepares the optical loss in mecopropP process.Test result is, the method that the embodiment of the present invention 4 the provides optical loss prepared in mecopropP process is 1.5%.
According to the method described in technique scheme, the purity of the mecopropP that the method that the test embodiment of the present invention 4 provides prepares and yield, test result is, purity >=97% of the mecopropP that the method that the embodiment of the present invention 4 provides prepares, yield counts 80.2% with S-2 chloropropionic acid, counts 90.2% with ortho-cresol.
As seen from the above embodiment, the invention provides a kind of preparation method of mecopropP, comprising: ortho-cresol and the first basic cpd are carried out the first reaction, obtains ortho-cresol salt; S-2 chloropropionic acid and the second basic cpd are carried out the second reaction, obtains chloropropionic acid salt; Described adjacent formate and described chloropropionic acid salt are carried out the 3rd reaction in toluene, obtains adjacent first phenoxy propionic acid; Under the effect of aminated compounds, hypochlorite and described adjacent first phenoxy propionic acid are carried out the 4th reaction, obtains mecopropP.Method provided by the invention adopts ortho-cresol and chloropropionic acid to prepare adjacent first phenoxy propionic acid in the basic conditions, then adopts hypochlorite to carry out chlorination the adjacent first phenoxy propionic acid obtained, and prepares mecopropP.The optics content of the mecopropP that this post chlorination processes provided by the invention prepares is higher.In addition, to prepare optical loss in the process of mecopropP less for method provided by the invention; Method provided by the invention can prevent the generation of dioxin, and the yield preparing mecopropP is higher; Preparation method's technique of mecopropP provided by the invention is simple, to the less pollution that environment produces.

Claims (10)

1. a preparation method for mecopropP, comprising:
Ortho-cresol and the first basic cpd are carried out the first reaction, obtains ortho-cresol salt;
S-2 chloropropionic acid and the second basic cpd are carried out the second reaction, obtains chloropropionic acid salt;
Described adjacent formate and described chloropropionic acid salt are carried out the 3rd reaction in toluene, obtains adjacent first phenoxy propionic acid;
Under the effect of aminated compounds, hypochlorite and described adjacent first phenoxy propionic acid are carried out the 4th reaction, obtains mecopropP.
2. method according to claim 1, is characterized in that, the temperature of described first reaction is 110 DEG C ~ 150 DEG C.
3. method according to claim 1, is characterized in that, the temperature of described second reaction is 10 DEG C ~ 80 DEG C.
4. method according to claim 1, is characterized in that, the temperature of described 3rd reaction is 110 DEG C ~ 130 DEG C.
5. method according to claim 1, is characterized in that, the temperature of described 4th reaction is 0 DEG C ~ 60 DEG C.
6. method according to claim 1, is characterized in that, the time of described 4th reaction is 1 hour ~ 10 hours.
7. method according to claim 1, is characterized in that, the pH value of described 4th reaction is 7 ~ 12.
8. method according to claim 1, is characterized in that, described aminated compounds is one or more in dimethyl formamide, ethanamide and propionic acid amide.
9. method according to claim 1, is characterized in that, described first basic cpd and the second basic cpd are independently selected from alkali metal hydroxide.
10. method according to claim 1, is characterized in that, the described 3rd reacted after, the 3rd reaction product obtained is extracted, reclaim obtain ortho-cresol salt.
CN201410617246.3A 2014-11-05 2014-11-05 Method for preparing purified 2-methyl-4-chloropropionic acid Pending CN104447288A (en)

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