CN111470994A - Preparation method of p-chlorobenzene glycine - Google Patents
Preparation method of p-chlorobenzene glycine Download PDFInfo
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- CN111470994A CN111470994A CN202010274969.3A CN202010274969A CN111470994A CN 111470994 A CN111470994 A CN 111470994A CN 202010274969 A CN202010274969 A CN 202010274969A CN 111470994 A CN111470994 A CN 111470994A
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/12—Formation of amino and carboxyl groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
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Abstract
The invention provides a preparation method of p-chlorobenzeneglycine, which comprises the steps of adding a mixed solution of a chloroform solution, a catalyst and p-chlorobenzaldehyde into a sodium hydroxide solution for mixing, dropwise adding liquid ammonia under stirring for 2-6 h; after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 5-10 hours at room temperature; after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine; the catalyst adopts trioctylmethylammonium chloride; the molar ratio of the p-chlorobenzaldehyde, the trioctylmethylammonium chloride, the chloroform, the sodium hydroxide and the ammonium bicarbonate is 1.0 (0.02-0.38), 1.5-2.5, (6.0-10.0) and (0.03-0.07). The invention has simple synthesis process, easily obtained raw materials and milder reaction, and avoids the toxicity and pollution of cyanide.
Description
Technical Field
The invention relates to the field of preparation of chlorophenylglycine, and in particular relates to a preparation method of p-chlorophenylglycine.
Background
P-chlorophenyl glycine (English: Chlorophenylglycine chemical formula: C)8H8CLNO2) The p-chlorophenylglycine also called D L-p-chlorophenylglycine has a melting point of 220-.
The method for synthesizing p-chlorobenzene glycine mainly comprises a biological method and a chemical method, wherein the chemical synthesis method mainly comprises the steps of preparing p-chlorobenzene hydantoin by taking p-chlorobenzaldehyde, sodium cyanide and ammonium bicarbonate as raw materials through a Bucherer-Bergs reaction, and then carrying out alkaline hydrolysis to prepare the p-chlorobenzene glycine. However, the process adopts the sodium cyanide method for production, a large amount of sodium cyanide is needed in the production, the toxicity is high, the labor protection condition is high, the environmental pollution is large, and the three wastes are strictly treated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide the preparation method of p-chlorophenyl glycine, which has the advantages of simple synthesis process, easily obtained raw materials, milder reaction and avoidance of the toxicity and pollution of cyanide.
According to one aspect of the present invention, there is provided a method for preparing p-chlorophenyl glycine, comprising the steps of:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 2-6 h;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 5-10 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts trioctylmethylammonium chloride;
the molar ratio of the p-chlorobenzaldehyde, the trioctylmethylammonium chloride, the chloroform, the sodium hydroxide and the ammonium bicarbonate is 1.0 (0.02-0.38), 1.5-2.5, 6.0-10.0 and 0.03-0.07;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated sulfuric acid with the concentration of 98% or concentrated hydrochloric acid with the concentration of 36%.
Preferably, the catalyst can also be any one of phase transfer catalysts of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride or quaternary phosphonium salt. Phase Transfer Catalysts (PTC) are a class of catalysts that can help transfer reactants from one Phase to another Phase where reactions can occur, thereby increasing the reaction rate of heterogeneous systems. In general, phase transfer catalyzed reactions exist, both in aqueous and organic solvent phases, ionic reactants tend to be soluble in the aqueous phase and insoluble in the organic phase, while organic substrates are soluble in the organic solvent. In the absence of a phase transfer catalyst, the two phases are isolated from each other, several reactants cannot come into contact, and the reaction proceeds very slowly. The presence of the phase transfer catalyst can combine with ions in the water phase (usually), and transfer reactants in the water phase into the organic phase by utilizing the affinity of the phase transfer catalyst to the organic solvent, so as to promote the reaction.
Preferably, the mother liquor is recovered for next reuse, and constitutes a mother liquor for recycling. Realizes the circulation balance of the mother liquor, has stable product yield, basically has no wastewater discharge in the synthesis process, and has good industrial application prospect.
Preferably, the molar ratio of the p-chlorobenzaldehyde to the trioctylmethylammonium chloride is 1.0: 0.35, the yield of the p-chlorobenzoyl glycine increases slightly with the increase of the catalyst dosage, but the dosage is increased continuously after the dosage is increased to a certain value, the yield is not improved greatly, and the yield of the p-chlorobenzoyl glycine is higher when the molar ratio of the p-chlorobenzoyl aldehyde to the trioctylmethylammonium chloride is 1.0: 0.35.
Preferably, the molar ratio of p-chlorobenzaldehyde to chloroform is 1.0: 2.5, chloroform is involved in the reaction as both a reactant and a solvent, and the yield of p-chlorobenzoyl glycine is high when the molar ratio of p-chlorobenzaldehyde to chloroform is 1.0: 2.5.
Preferably, the molar ratio of the p-chlorobenzaldehyde to the sodium hydroxide is 1.0: 6.0, the yield of the p-chlorobenzaldehyde and the sodium hydroxide is increased along with the increase of the amount of the sodium hydroxide, and then the yield of the p-chlorobenzaldehyde and the sodium hydroxide is reduced along with the increase of the amount of the sodium hydroxide, because the appropriate sodium hydroxide can ensure that the generation speed of the dichlorocarbene matches with the reaction speed of the acceptor, while the excessive sodium hydroxide not only ensures that the generation speed of the dichlorocarbene is higher than the reaction speed of the acceptor, but also causes other reactions, and concentrated alkali can cause a plurality of side reactions, and when the molar ratio of the p-chlorobenzaldehyde to the sodium hydroxide is 1.0: 6.0, the yield of the p-chlorobenzaldehyde and the sodium hydroxide is higher.
Preferably, the molar ratio of the p-chlorobenzaldehyde to the ammonium bicarbonate is 1.0: 0.05.
Preferably, the reaction time of the step three at room temperature is 8 hours, and the yield of the p-chlorophenyl glycine increases with the increase of the reaction time, but the increase gradually becomes smaller.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the preparation method of p-chlorobenzoyl glycine, a reaction liquid consisting of p-chlorobenzoyl aldehyde, chloroform, ammonia water and sodium hydroxide is an organic phase-water phase, a phase transfer catalyst is utilized to catalyze and help a reactant to be transferred from one phase to another phase capable of reacting to synthesize the p-chlorobenzoyl glycine, so that the increase of side reactions caused by the same phase of strong base and aldehyde is avoided, and in the two phases, dichlorocarbene is generated in the water phase and enters the organic phase to react with the aldehyde, so that the reaction is more specific and stable, meanwhile, water is used as a solvent, the requirement of an anhydrous organic solvent is abandoned, the reaction is milder, and the toxicity and pollution of cyanide are avoided;
(2) according to the preparation method of p-chlorophenyl glycine, the addition of the phase transfer catalyst accelerates the reaction rate, the reactants are fully contacted, the reaction is relatively thorough, the product yield is high, the synthesis operation is simple and convenient, the temperature and pressure are reduced, the intensity required by equipment is low, the operation is relatively simple, and the use of dangerous reagents required by a conventional method is avoided;
(3) the preparation method of p-chlorophenyl glycine avoids the use of sodium cyanide with high toxicity, and has the advantages of simple synthesis process, easily obtained raw materials and low cost investment;
(4) the preparation method of p-chlorophenyl glycine, which is related by the invention, realizes the circulation balance of the mother liquor, has stable product yield, basically no wastewater discharge in the synthesis process, and has good industrial application prospect;
(5) the preparation method of p-chlorophenylglycine has the advantages of simple reaction, ingenious design, obvious effect, low cost and strong practicability, and is suitable for large-scale popularization.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
The embodiment provides a preparation method of p-chlorophenylglycine, which comprises the following steps:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 2 hours;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 8 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts trioctylmethylammonium chloride;
the molar ratio of the p-chlorobenzaldehyde to the trioctylmethylammonium chloride to the chloroform to the sodium hydroxide to the ammonium bicarbonate is 1.0:0.02:1.5:6.0: 0.03;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated sulfuric acid with the concentration of 98%.
Example 2
The embodiment provides a preparation method of p-chlorophenylglycine, which comprises the following steps:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 4 hours;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 6 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts tetrabutylammonium bromide;
the molar ratio of the p-chlorobenzaldehyde to the tetrabutylammonium bromide to the chloroform to the sodium hydroxide to the ammonium bicarbonate is 1.0:0.025:1.8:8.0: 0.04;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated sulfuric acid with the concentration of 98%.
Example 3
The embodiment provides a preparation method of p-chlorophenylglycine, which comprises the following steps:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 4 hours;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 8 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts benzyltriethylammonium chloride;
the molar ratio of the p-chlorobenzaldehyde to the benzyltriethylammonium chloride to the chloroform to the sodium hydroxide to the ammonium bicarbonate is 1.0:0.035:2.0:8.0: 0.06;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated sulfuric acid with the concentration of 98%.
Example 4
The embodiment provides a preparation method of p-chlorophenylglycine, which comprises the following steps:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 6 hours;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 5 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts benzyltriethylammonium chloride;
the molar ratio of the p-chlorobenzaldehyde to the benzyltriethylammonium chloride to the chloroform to the sodium hydroxide to the ammonium bicarbonate is 1.0:0.038:2.5:10.0: 0.07;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated hydrochloric acid with the concentration of 36%.
Example 5
The embodiment provides a preparation method of p-chlorophenylglycine, which comprises the following steps:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 6 hours;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 5 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts benzyltriethylammonium chloride;
the molar ratio of the p-chlorobenzaldehyde to the benzyltriethylammonium chloride to the chloroform to the sodium hydroxide to the ammonium bicarbonate is 1.0:0.02:1.5:6.0: 0.03;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated sulfuric acid with the concentration of 98%.
Example 6
The embodiment provides a preparation method of p-chlorophenylglycine, which comprises the following steps:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 2 hours;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 10 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts tetradecyl trimethyl ammonium chloride;
the molar ratio of the p-chlorobenzaldehyde to the tetradecyl trimethyl ammonium chloride to the chloroform to the sodium hydroxide to the ammonium bicarbonate is 1.0:0.03:2.0:8.0: 0.05;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated hydrochloric acid with the concentration of 36%.
Examples 1 to 6 have the following advantageous effects:
(1) the method is characterized in that a reaction liquid consisting of p-chlorobenzaldehyde, chloroform, ammonia water and sodium hydroxide is an organic phase-water phase, a phase transfer catalyst is utilized to catalyze and help reactants to be transferred from one phase to another phase which can react to synthesize p-chlorobenzeneglycine, so that the side reaction increase caused by the co-position of strong base and aldehyde in the same phase is avoided, and in the two phases, dichlorocarbene is generated in the water phase and enters the organic phase to react with the aldehyde, so that the reaction is more specific and stable, meanwhile, water is used as a solvent, the requirement of an anhydrous organic solvent is eliminated, the reaction is milder, and the toxicity and pollution of cyanide are avoided;
(2) the addition of the phase transfer catalyst accelerates the reaction rate, the reactants are fully contacted, the reaction is relatively thorough, the product yield is high, the synthesis operation is simple and convenient, the temperature and the pressure are reduced, the intensity required by equipment is low, the operation is relatively simple, and the use of dangerous reagents required by the conventional method is avoided;
(3) the method avoids the use of sodium cyanide with high toxicity, has simple synthesis process, easily obtained raw materials and low cost investment;
(4) the method realizes the circulation balance of the mother liquor, has stable product yield, basically has no wastewater discharge in the synthesis process, and has good industrial application prospect;
(5) the reaction is simple, the design is ingenious, the effect is obvious, the cost is low, the practicability is strong, and the method is suitable for large-scale popularization.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (8)
1. The preparation method of the p-chlorobenzene glycine is characterized by comprising the following steps:
adding a catalyst and p-chlorobenzaldehyde into a chloroform solution, and accelerating the dissolution of the catalyst and the p-chlorobenzaldehyde in the chloroform by oscillation to prepare a mixed solution;
step two, adding the mixed solution prepared in the step one into a sodium hydroxide solution for mixing, and dropwise adding liquid ammonia under stirring for 2-6 h;
step three, after the dropwise addition of the liquid ammonia is finished, adding an ammonium bicarbonate solution, and reacting for 5-10 hours at room temperature;
after the reaction is finished, distilling and concentrating the reaction solution, decoloring and filtering the reaction solution by using activated carbon, adjusting the pH value of the filtrate to 6.0 by using inorganic acid, cooling and filtering the filtrate to obtain a crude product and a mother solution, washing the crude product by using water, ethanol and ether, and drying the washed crude product to obtain a finished product of p-chlorophenyl glycine;
the catalyst adopts trioctylmethylammonium chloride;
the molar ratio of the p-chlorobenzaldehyde, the trioctylmethylammonium chloride, the chloroform, the sodium hydroxide and the ammonium bicarbonate is 1.0 (0.02-0.38), 1.5-2.5, 6.0-10.0 and 0.03-0.07;
the dropping speed of the liquid ammonia is 2 drops/second;
the inorganic acid is concentrated sulfuric acid with the concentration of 98% or concentrated hydrochloric acid with the concentration of 36%.
2. The method for preparing p-chlorophenylglycine as claimed in claim 1, wherein the catalyst is any one of tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydrogen sulfate, benzyltriethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride or quaternary phosphonium salt.
3. The method for preparing p-chlorophenylglycine as claimed in claim 1, wherein the mother liquor is recovered for reuse next time, thereby recycling the mother liquor.
4. The method for preparing p-chlorophenylglycine as claimed in claim 1, wherein the molar ratio of p-chlorobenzaldehyde to trioctylmethylammonium chloride is 1.0: 0.35.
5. The method for preparing p-chlorophenylglycine as claimed in claim 1, wherein the molar ratio of p-chlorobenzaldehyde to chloroform is 1.0: 2.5.
6. The method for preparing p-chlorophenylglycine as claimed in claim 1, wherein the molar ratio of p-chlorobenzaldehyde to sodium hydroxide is 1.0: 6.0.
7. The method for preparing p-chlorophenylglycine as claimed in claim 1, wherein the molar ratio of p-chlorobenzaldehyde to ammonium bicarbonate is 1.0: 0.05.
8. The method for preparing p-chlorophenylglycine as claimed in claim 1, wherein the reaction time in step three at room temperature is 8 hours.
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Application publication date: 20200731 |