CN109824531A - A method of continuous quickly preparation DL- phenylglycine and the like - Google Patents
A method of continuous quickly preparation DL- phenylglycine and the like Download PDFInfo
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Abstract
The present invention, which provides, a kind of continuous quickly prepares DL- phenylglycine and its similar method, it include: that micro passage reaction is added with carbon ammonium aqueous solution in 2- hydroxy-benzyl cyanide and the like (abbreviation cyanalcohol) to react, controlling reaction temperature is 80~130 DEG C, pressure is 0.5~2.0MPa, reactant residence time in microchannel is 1~8min, obtains 5- phenyl-hydantoins and the like (abbreviation glycolylurea) aqueous solution；Micro passage reaction is added with alkali in glycolylurea to react, controlling reaction temperature is 120~200 DEG C, pressure is 1.0~3.5MPa, residence time of the reactant in microchannel is 1~8min, obtain phenylglycine and the like saline solution, acidified neutralization, crystallization, obtain phenylglycine and the like.The present invention uses micro passage reaction, substantially reduces the reaction time, accelerates reaction rate, reduces cyanalcohol pyrolysis polymerization, and no coupling product generates, and product yield is high, and clean and environmental protection reduces production cost.
Description
Technical field
The present invention relates to chemical field, in particular to a kind of continuous side for quickly preparing DL- phenylglycine and the like
Method.
Background technique
DL- phenylglycine and its derivative are a kind of important medical synthetic intermediates, mainly for the preparation of beta-lactam
Class antibiotic, polypeptide hormone and pesticide.Begin to batch production DL- phenylglycine the external sixties, China is in ability at the beginning of the eighties
It realizes the industrialized production of DL- phenylglycine, and mainly uses sodium cyanide method.The method is using benzaldehyde as primary raw material, with cyaniding
Reaction synthesis DL- phenylglycine, the DL- phenylglycine that the method obtains under phase transfer catalyst effect such as sodium and solid ammonium salt
Poor product quality, color are compared with the disadvantages of deep, yield is low, by-product inorganic salts are more.
DL- phenylglycine and its derivative another synthetic method are using phase transfer catalyst, based on benzaldehyde
Raw material is wanted, is reacted with chloroform, sodium hydroxide, ammonium hydrogen carbonate, one-step synthesis DL- phenylglycine.The production technology yield is low, only
46%, and generate the inorganic salts of a large amount of brine wastes and low value.
And the synthesis technology of DL-p-hydroxyphenylglycine is used with phenol and glyoxalic acid, water, 4- nitro neighbour benzene two mostly
For carboximide under the action of Phase-transfer catalyst quaternary ammonium salt, one pot reaction preparation, synthesis procedure is complex, and DL- is to hydroxyl
Base phenylglycine yield is lower.DL-p-hydroxyphenylglycine obtains D-pHPG by splitting.D- para hydroxybenzene
Glycine is mainly used as semisynthetic penicillin and semi-synthetic head embraces the side chain compound of bacteriums drug.The main medicine produced with it
Product have through ammonia section penicillin (Amoxicillin), through ammonia section penicillin Clavulanate, light ammonia section header armful, light ammonia choker bar head armful, head
Croak ketone, head armful bent throat etc. is embraced, these medicinal usages are extensive, to gram-positive bacteria, Gram-negative bacteria, toxoplasm, conveyor screw
Deng there is killing effect;It is also applied to photosensitive field and the analytical reagent as iron, phosphorus, silicon etc. etc..The external seventies, that is, large quantities of
Amount production D-pHPG, produces for Amoxicillin.In recent years, developed countries' annual requirement such as America and Europe ten thousand tons with
On.Larger side chain compound D-pHPG supplier is Dutch DSM N. V., Spain in the world
Also there are kiloton scale production unit in DeriVados company etc., Singapore.
The production technology of DL- phenylglycine and its current mainstream of derivative be with benzaldehyde and the like, Cymag (or
Person's potassium cyanide) and ammonium chloride be that " one kettle way " Strecker of raw material reacts, i.e. formaldehyde and the like, Cymag (or cyanogen
Change potassium) and ammonium chloride hybrid reaction obtain 2- amino-benzene acetonitrile analog (abbreviation cyanamide), then acidolysis or alkaline hydrolysis again, obtain
To DL- phenylglycine and its derivative.However, at present using Cymag, ammonium chloride and benzaldehyde and its one kettle way of derivative
Aniline cyanogen analog is prepared, not only yield is low, and generates a large amount of reluctant cyanide wastewater.In addition to this, also
Following two glycolylurea method technique.
One is " two components " cyanalcohol glycolylurea methods, i.e., with hydrogen cyanide and benzaldehyde and the like for Material synthesis 2- hydroxyl
Base-benzene acetonitrile or 2- hydroxy-benzyl cyanide analog (abbreviation cyanalcohol), cyanalcohol synthesize glycolylurea aqueous solution again, glycolylurea alkaline hydrolysis, acid again
Change obtains product.If patent CN106380415A discloses a kind of D, the preparation method of L- phenylglycine and the like be with
Benzaldehyde and the like, hydrogen cyanide are raw material, generate 2- hydroxy-benzyl cyanide or 2- hydroxy-benzyl cyanide by cyanogenation
Analog (abbreviation cyanalcohol), the cyanalcohol reactant aqueous solution with carbon dioxide and ammonia again generate 5- phenyl-hydantoins and its similar
Object (abbreviation glycolylurea)；Glycolylurea is stripped, then is made through alkaline hydrolysis, stripping, decoloration, neutralization, crystallization, washing, centrifugation, drying and other steps
D, L- phenylglycine and the like.Although using cyanalcohol in the patent, the receipts of phenylglycine and the like are substantially increased
Rate, but be finally unavoidably to generate a large amount of sodium chloride or sodium sulphate, and a large amount of reluctant brine waste is
A kind of production technology of unclean environmental protection.
Another be using benzaldehyde and the like, Cymag, carbon ammonium aqueous solution as raw material " three components " glycolylurea method,
The glycolylurea aqueous solution of containing sodium carbonate, the sea are prepared using benzaldehyde and the like, Cymag, carbon ammonium aqueous solution as raw material
Because aqueous solution obtains product by alkaline hydrolysis, acidification.As patent CN106083628B is disclosed and a kind of system of p-chlorophenylglycine
Preparation Method is reacted completely in micro passage reaction with p-chlorobenzaldehyde, ammonium hydrogen carbonate and Cymag, then uses tubular reactor
Prepare p-chlorophenylglycine.Its main feature is that raw material is intermediate by carrying out cyclization preparation in micro passage reaction through flow gauge
Body is to chlorobenzene glycolylurea, then intermediate is carried out alkaline hydrolysis by tubular reactor through flow gauge and prepares p-chlorophenylglycine sodium,
Reaction can be completed within 8-18 minutes in total, finally imports in reaction flask and carry out acidification crystallization processing.Product purity is in 98 .0%
More than, yield is 95% or more.There are also described in CN103086905B for the patent of similar approach.Although in such methods, using cyanogen
Change sodium as cyanogen source, but be finally unavoidably generate a large amount of sodium chloride or sodium sulphate, and largely it is reluctant
Brine waste, and a kind of production technology of unclean environmental protection.
In conclusion preparation method either " one kettle way " Strecker of DL- phenylglycine and its derivative is anti-at present
Should or cyanalcohol glycolylurea method, either " three components " glycolylurea method, all have that preparation method is complicated, the production cycle is long, the reaction time
Long, side reaction is more, and product yield is low, of poor quality, color is compared with deep, by-product inorganic salts are more, not environmentally protective, a large amount of brine wastes rows
It puts, the problems such as poor product quality.
Summary of the invention
In view of the foregoing deficiencies of prior art, the purpose of the present invention is to provide a kind of continuous quickly preparation DL- benzene
The method of glycine and the like prepares DL- phenylglycine and the like the reaction time for solving in the prior art
Length, reaction rate are slow, and raw material cyanide is easy to happen thermal polymerization and generates by-product, easily lead to foreign pigment generation, generate greatly
The problems such as a large amount of low value inorganic salts of the cyanide wastewater or by-product of amount and a large amount of reluctant brine wastes.
In order to achieve the above objects and other related objects, first aspect present invention provides a kind of continuous quickly preparation DL- benzene
Glycine and its similar method, comprising: 2- hydroxy-benzyl cyanide and the like (abbreviation cyanalcohol) and carbon ammonium aqueous solution are added
Micro passage reaction is reacted, and control reaction temperature is 80~130 DEG C, and pressure is 0.5~2.0MPa, and reactant is in microchannel
The interior residence time is 1~8min, obtains 5- phenyl-hydantoins and the like (abbreviation glycolylurea) aqueous solution；By glycolylurea and alkali
Micro passage reaction is added to be reacted, control reaction temperature is 120~200 DEG C, and pressure is 1.0~3.5MPa, and reactant exists
Residence time in microchannel is 1~8min, obtains phenylglycine and the like saline solution, acidified neutralization, crystallization obtain
Arrive phenylglycine and the like.
2. according to the method described in claim 1, it is characterized by: described 2- hydroxy-benzyl cyanide and the like,
Its general formula of the chemical structure of 5- phenyl-hydantoins and the like and DL- phenylglycine and the like is as follows:
In formula R group be phenyl ring on ortho position, meta or para position, R group be one of hydrogen atom, chlorine atom, fluorine atom or
Person is a variety of；Described-hydroxy-benzyl cyanide and the like is liquid or solid-state, mass percentage be 70wt%~
99wt%, in described 5- phenyl-hydantoins and the like aqueous solution, the quality of 5- phenyl-hydantoins and the like
Percentage composition is 10wt%~50wt%, in described phenylglycine and the like saline solution, phenylglycine and the like
Mass percentage is 10wt%~40wt%.
In some embodiments of the invention, described 2- hydroxy-benzyl cyanide and the like (abbreviation cyanalcohol) and ammonium bicarbonate water
Solution molar ratio are as follows: cyanalcohol/ammonia/carbon dioxide=1:1.5~2.0:1.0~1.5, control reaction temperature are 100~130
DEG C, pressure is 0.5~1.5MPa, and reactant residence time in microchannel is 2~5min, in carbon ammonium aqueous solution, the quality of ammonia
Percentage composition is 5wt%~10wt%, and the mass percentage of carbon dioxide is 8wt%~19.5wt%.
In some embodiments of the invention, the alkali be selected from sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide,
At least one of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, particularly preferred wet chemical, mass percentage are
30wt%~55wt%.
In some embodiments of the invention, described 5- phenyl-hydantoins and the like (abbreviation glycolylurea) and carbonic acid
The molar ratio of potassium are as follows: glycolylurea/potassium ion=1:1.2~2.5, control reaction temperature be 160~180 DEG C, pressure be 1.5~
2.5MPa, residence time of the reactant in microchannel are 2~8min.
In some embodiments of the invention, the acidulant is selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, carbonic acid, dioxy
Change at least one of carbon etc., particularly preferred carbon dioxide, being passed through carbon dioxide souring temperature is 10~30 DEG C, pressure 0.1
~0.6MPa, acidification terminal pH are 7.0~8.5.
In some embodiments of the invention, in described phenylglycine and the like sylvite aqueous solution, ammonia content is lower than
50ppm, the mass percentage of potassium ion are 6.0wt%~11.5wt%.
In some embodiments of the invention, the acidizing crystal mother liquor is the carbonic acid containing phenylglycine and the like
In hydrogen aqueous solutions of potassium, the mass percentage of phenylglycine and the like is 2wt%~10wt%, the quality percentage of saleratus
Content is 10wt%~25wt%, which obtains potassium carbonate and phenylglycine and the like potassium after heating decarburization, concentration
The mixed aqueous solution of salt is recycled to 5- phenyl-hydantoins and the like hydrolysis, after concentration, potassium ion quality hundred in mother liquor
Content is divided to be not less than 20wt%.
In some embodiments of the invention, the potassium ion and the (5- phenyl-hydantoins and the like+sweet ammonia of benzene
Acid and the like) molar ratio be 1.2~2.5:1.0, control reaction temperature be 160~180 DEG C, pressure be 1.5~
2.5MPa, residence time of the reactant in microchannel are 2~8min.
Second aspect of the present invention provides above method preparation DL- phenylglycine and the like, the DL- phenylglycine
And the like selected from DL- phenylglycine, DL- o-chlorobenzene glycine, chlorophenyl glycine, DL- p-chlorophenylglycine, DL- between DL-
Between at least one of fluorophenyl glycine etc. fluorophenyl glycine, DL- o fluorobenzaldehyde, DL-.
As described above, a kind of continuous method for quickly preparing DL- phenylglycine and the like of the invention, has following
The utility model has the advantages that the present invention uses micro passage reaction, glycolylurea preparation and alkaline hydrolysis time are greatly shortened, reaction is accelerated to carry out, is reduced
Cyanalcohol pyrolysis polymerization, no coupling product generates and brine waste generates, and product yield is high, and clean and environmental protection reduces production cost.
Present invention solution prepares that DL- phenylglycine and the like the reaction time is long, reaction rate is slow in the prior art,
Raw material cyanide be easy to happen thermal polymerization and generate by-product, easily lead to foreign pigment generate, generate a large amount of cyanide wastewater or
The problems such as a large amount of low value inorganic salts of person's by-product and a large amount of reluctant brine wastes.
Specific embodiment
Illustrate embodiments of the present invention below by way of specific specific example, those skilled in the art can be by this specification
Other advantages and efficacy of the present invention can be easily understood for disclosed content.The present invention can also pass through in addition different specific realities
The mode of applying is embodied or practiced, the various details in this specification can also based on different viewpoints and application, without departing from
Various modifications or alterations are carried out under spirit of the invention.
The manufacturer of the micro passage reaction used in following embodiment is Mainz, Germany microtechnology research institute IMM, type
Number SIMM-V2-SS, microchannel internal diameter are 50 μm.
The reactant form of following embodiment is liquid, it should be noted that reactant is not limited by form, can also be with
For other forms such as gaseous state, can make 2- hydroxy-benzyl cyanide and the like and carbon ammonium aqueous solution or and its 5- phenyl-second in
Uride and the like (abbreviation glycolylurea) aqueous solution and alkali smoothly react in micro passage reaction.
Embodiment 1
The preparation of DL- phenylglycine:
By mass percentage be 80wt% 166.4338 grams of 2- hydroxy-benzyl cyanide aqueous solution (cyanalcohol) (1.0 moles) and ammonia and
Carbon dioxide content be respectively 7.5wt% and 14.56wt% 453.3333 grams of carbon ammonium aqueous solution (cyanalcohol: ammonia: carbon dioxide=
1.0:2.0:1.5) it is pumped into micro passage reaction by metering pump simultaneously, flow velocity of the cyanalcohol in microchannel is 10.0g/min,
Flow velocity of the carbon ammonium aqueous solution in microchannel is 27.238g/min, and the temperature for controlling reaction is 120 DEG C, pressure 1.5MPa, is stopped
Staying the time is the time that 3min(i.e. reaction solution flows through microchannel), the liquid of outflow is in the transparent 5- phenyl-second of clear, colorless
Uride aqueous solution (glycolylurea) obtains glycolylurea aqueous solution and amounts to 589.7670 grams, wherein 5- phenyl-by deamination and carbon dioxide
Hydantoins content is 29.87wt%, and 5- phenyl-hydantoins yield is greater than 99.9%(in terms of cyanalcohol).
The potassium carbonate for being 50wt% by 5- phenyl obtained above-hydantoins aqueous solution (glycolylurea) and mass percentage
276 grams of aqueous solution (glycolylurea: potassium ion=1.0:2.0) is pumped into micro passage reaction by metering pump simultaneously, glycolylurea microchannel again
In flow velocity be 58.9g/min, flow velocity of the wet chemical in microchannel is 27.6g/min, and the temperature for controlling reaction is
178 DEG C, pressure 2.5MPa, residence time are the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow is clarification
Pale yellow transparent liquid, the liquid pass through deamination and carbon dioxide, obtain phenylglycine aqueous solutions of potassium 458.8235g, wherein benzene is sweet
The mass percentage of propylhomoserin is 32.94wt%, and potassium ion mass percentage is 17.0wt%, and the yield of phenylglycine is
99.9% or more.It is 8.5wt% by the content that obtained hydrolyzate is diluted with water to potassium ion, the content of phenylglycine is
16.47wt% obtains 917.647g hydrolyzate after dilution.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.2MPa, in
It is 20 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 8.0, filter out solid, wash,
Drying obtains phenylglycine product 115.6860g, and main content is 98wt%, the product be it is powdered, by recrystallization operation, obtain
To the DL- phenylglycine product of lenticular, purity reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filtrate is to contain benzene
The potassium bicarbonate aqueous solution of glycine, the quality of filtrate are 901.78g, and wherein potassium ion mass percentage is 8.65wt%, benzene
The mass percentage of glycine is 4.2wt%, which is by heating decarburization, being concentrated into potassium ion mass percentage
Lower batch glycolylurea hydrolysis is recycled to after 28.5wt% or so, the mother liquor quality obtained after decarburization, concentration is 273.698g.
Embodiment 2
The preparation (potassium carbonate Recycling Mother Solution) of DL- phenylglycine:
By mass percentage be 80wt% 166.4338 grams of 2- hydroxy-benzyl cyanide aqueous solution (cyanalcohol) (1.0 moles) and ammonia and
Carbon dioxide content be respectively 7.5wt% and 13.59wt% 340.0 grams of carbon ammonium aqueous solution (cyanalcohol: ammonia: carbon dioxide=1.0:
It 1.5:1.05) is pumped into micro passage reaction by metering pump simultaneously, flow velocity of the cyanalcohol in microchannel is 10.0g/min, carbon
Flow velocity of the aqueous ammonium in microchannel is 20.43g/min, and the temperature for controlling reaction is 110 DEG C, pressure 1.2MPa, is stopped
Time is the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow is acyl in the transparent 5- phenyl-second of clear, colorless
Urea aqueous solution (glycolylurea) obtains glycolylurea aqueous solution and amounts to 450.550 grams, wherein in 5- phenyl-second by deamination and carbon dioxide
Ureide content is 39.10wt%, and 5- phenyl-hydantoins yield is greater than 99.9%(in terms of cyanalcohol).
Contain phenylglycine potassium for what 5- phenyl obtained above-hydantoins aqueous solution (glycolylurea) and embodiment 1 recycled
Wet chemical 273.698g(wherein potassium ion be 28.76wt%；Phenylglycine content is 13.838wt%) and add
Mass percentage be 50wt% 75.348 grams of wet chemical ((glycolylurea+phenylglycine): potassium ion=1.0:2.0) simultaneously
It is pumped into micro passage reaction by metering pump, the flow velocity in microchannel is 58.9g/min to glycolylurea again, and wet chemical is micro-
Flow velocity in channel is 45.63g/min, and the temperature for controlling reaction is 178 DEG C, pressure 2.5MPa, and the residence time is for 4min(
Reaction solution flows through the time of microchannel), the liquid of outflow is clear light yellow transparent liquid, which passes through deamination and titanium dioxide
Carbon obtains phenylglycine aqueous solutions of potassium 458.8235g, and wherein the mass percentage of phenylglycine is 41.94wt%, potassium ion
Mass percentage is 21.64wt%, and the yield of phenylglycine is 99.9% or more, which, which is diluted to potassium content, is
9.5wt%, phenylglycine content are 18.41wt%, and aqueous solution amounts to 1045.20g.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.2MPa, in
It is 25 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 8.0, filter out solid, wash,
Drying obtains phenylglycine product 147.2682g, and main content is 98wt%, the product be it is powdered, by recrystallization operation (weight
The recrystallization mother liquor that crystallization solution is recycled using embodiment 1 and the water added), the DL- phenylglycine product of lenticular is obtained, it is pure
Degree reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filtrate is the potassium bicarbonate aqueous solution containing phenylglycine, filtrate
Quality be 940.890g, wherein potassium ion mass percentage is 10.55wt%, and the mass percentage of phenylglycine is
5.11wt%, the filtrate are recycled to down after heating decarburization, being concentrated into potassium ion mass percentage as 28.5wt% or so and criticize
Secondary glycolylurea hydrolysis, the mother liquor quality obtained after decarburization, concentration are 348.4778g.
Embodiment 3
The preparation of DL- o-chlorobenzene glycine:
By mass percentage be 90wt% 2- hydroxyl -186.2133 grams of neighbour chlorobenzene acetonitrile aqueous solution (cyanalcohol) (1.0 moles) and
Ammonia and carbon dioxide content are respectively 453.3333 grams of the carbon ammonium aqueous solution (cyanalcohol: ammonia: carbon dioxide of 7.5wt% and 14.56wt%
=1.0:2.0:1.5) it is pumped into micro passage reaction by metering pump simultaneously, flow velocity of the cyanalcohol in microchannel is 10.0g/
Min, flow velocity of the carbon ammonium aqueous solution in microchannel are 27.238g/min, and the temperature for controlling reaction is 120 DEG C, pressure is
1.5MPa, residence time are the time that 3min(, that is, reaction solution flows through microchannel), the liquid of outflow is the transparent 5- of clear, colorless
(Chloro-O-Phenyl)-hydantoins aqueous solution (glycolylurea) obtains glycolylurea aqueous solution total 595.5466 by deamination and carbon dioxide
Gram, wherein 5-(Chloro-O-Phenyl)-hydantoins content is 35.37wt%, 5-(Chloro-O-Phenyl)-hydantoins yield is greater than 99.9%
(in terms of cyanalcohol).
The carbon for being 50wt% by 5- Chloro-O-Phenyl obtained above-hydantoins aqueous solution (glycolylurea) and mass percentage
276 grams of sour aqueous solutions of potassium (glycolylurea: potassium ion=1.0:2.0) is pumped into micro passage reaction by metering pump simultaneously, and glycolylurea is micro- again
Flow velocity in channel is 58.9g/min, and flow velocity of the wet chemical in microchannel is 27.30g/min, controls the temperature of reaction
Degree is 178 DEG C, pressure 2.5MPa, and the residence time is the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow is
Clear light yellow transparent liquid, the liquid pass through deamination and carbon dioxide, obtain o-chlorobenzene glycine aqueous solutions of potassium 478.8255g,
Wherein the mass percentage of o-chlorobenzene glycine is 38.76wt%, and potassium ion mass percentage is 16.29wt%, adjacent chlorobenzene
The yield of glycine is 99.9% or more.It is 9.0wt% by the content that obtained hydrolyzate is diluted with water to potassium ion, adjacent chlorobenzene is sweet
The content of propylhomoserin is 21.41wt%, and 866.6742g hydrolyzate is obtained after dilution.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.3MPa, in
It is 20 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 8.2, filter out solid, wash,
Drying obtains o-chlorobenzene glycine product 151.5167g, and main content is 98wt%, the product be it is powdered, grasped by recrystallization
Make, obtain the DL- o-chlorobenzene glycine product of lenticular, purity reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filter
Liquid is the potassium bicarbonate aqueous solution containing o-chlorobenzene glycine, and the quality of filtrate is 858.5740g, wherein potassium ion quality percentage
Content is 9.08wt%, and the mass percentage of o-chlorobenzene glycine is 4.32wt%, and the filtrate is by heating decarburization, being concentrated into potassium
Mass of ion percentage composition is recycled to lower batch glycolylurea hydrolysis, the mother liquor quality obtained after decarburization, concentration after being 28.5wt% or so
For 273.5387g.
Embodiment 4
The preparation of DL- p-chlorophenylglycine:
Mass percentage is first for 2- hydroxyl-(1.0 moles) of 223.4560 grams of neighbour's chlorobenzene acetonitrile aqueous solution (cyanalcohol) of 75wt%
60 DEG C are preheated to, is then again respectively 340.0 grams of carbon ammonium aqueous solution of 7.5wt% and 13.59wt% with ammonia and carbon dioxide content
(cyanalcohol: ammonia: carbon dioxide=1.0:1.5:1.05) is pumped into micro passage reaction by metering pump simultaneously, and cyanalcohol is in microchannel
In flow velocity be 10.0g/min, flow velocity of the carbon ammonium aqueous solution in microchannel is 15.22g/min, and the temperature for controlling reaction is
100 DEG C, pressure 1.0MPa, residence time are the time that 5min(, that is, reaction solution flows through microchannel), the liquid of outflow is clarification
Colorless and transparent 5-(rubigan)-hydantoins aqueous solution (glycolylurea) by deamination and carbon dioxide obtains glycolylurea aqueous solution
Total 545.5466 grams, wherein 5-(rubigan)-hydantoins content is 38.61wt%, 5-(rubigan)-hydantoins
Yield is greater than 99.9%(in terms of cyanalcohol).
By 5-(rubigan obtained above)-hydantoins aqueous solution (glycolylurea) and mass percentage be 50wt%'s
207 grams of wet chemical (glycolylurea: potassium ion=1.0:1.5) is pumped into micro passage reaction by metering pump simultaneously, and glycolylurea is again
Flow velocity in microchannel is 58.9g/min, and flow velocity of the wet chemical in microchannel is 22.35g/min, controls reaction
Temperature is 178 DEG C, pressure 2.5MPa, and the residence time is the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow
For clear light yellow transparent liquid, which passes through deamination and carbon dioxide, obtains p-chlorophenylglycine aqueous solutions of potassium 598.550g,
Wherein the mass percentage of p-chlorophenylglycine is 31.0wt%, and potassium ion mass percentage is 9.8wt%, to the sweet ammonia of chlorobenzene
The yield of acid is 99.9% or more.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.3MPa, in
It is 30 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 8.2, filter out solid, wash,
Drying obtains p-chlorophenylglycine product 123.1074g, and main content is 98wt%, the product be it is powdered, grasped by recrystallization
Make, obtain the DL- p-chlorophenylglycine product of lenticular, purity reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filter
Liquid is the potassium bicarbonate aqueous solution containing p-chlorophenylglycine, and the quality of filtrate is 580.5560g, wherein potassium ion quality percentage
Content is 10.1wt%, and the mass percentage of p-chlorophenylglycine is 11.19wt%, and the filtrate is by heating decarburization, being concentrated into
Potassium ion mass percentage is recycled to lower batch glycolylurea hydrolysis, the mother liquor matter obtained after decarburization, concentration after being 28.5wt% or so
Amount is 205.8710g.
Embodiment 5
The preparation of chlorophenyl glycine between DL-:
By mass percentage be 90wt% 186.2133 grams of 2- hydroxyl-chlorobenzene acetonitrile aqueous solution (cyanalcohol) (1.0 moles) with
Ammonia and carbon dioxide content are respectively 453.3333 grams of the carbon ammonium aqueous solution (cyanalcohol: ammonia: carbon dioxide of 7.5wt% and 14.56wt%
=1.0:2.0:1.5) it is pumped into micro passage reaction by metering pump simultaneously, flow velocity of the cyanalcohol in microchannel is 10.0g/
Min, flow velocity of the carbon ammonium aqueous solution in microchannel are 27.238g/min, and the temperature for controlling reaction is 120 DEG C, pressure is
1.5MPa, residence time are the time that 3min(, that is, reaction solution flows through microchannel), the liquid of outflow is the transparent 5- of clear, colorless
(chlorphenyl)-hydantoins aqueous solution (glycolylurea) obtains glycolylurea aqueous solution total 595.5466 by deamination and carbon dioxide
Gram, wherein chlorphenyl between 5-()-hydantoins content is 35.37wt%, chlorphenyl between 5-()-hydantoins yield is greater than 99.9%
(in terms of cyanalcohol).
The carbon for being 50wt% by chlorphenyl between 5- obtained above-hydantoins aqueous solution (glycolylurea) and mass percentage
276 grams of sour aqueous solutions of potassium (glycolylurea: potassium ion=1.0:2.0) is pumped into micro passage reaction by metering pump simultaneously, and glycolylurea is micro- again
Flow velocity in channel is 58.9g/min, and flow velocity of the wet chemical in microchannel is 27.30g/min, controls the temperature of reaction
Degree is 178 DEG C, pressure 2.5MPa, and the residence time is the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow is
Clear light yellow transparent liquid, the liquid pass through deamination and carbon dioxide, obtain a chlorophenyl glycine aqueous solutions of potassium 478.8255g,
The mass percentage of in-between chlorophenyl glycine is 38.76wt%, and potassium ion mass percentage is 16.29wt%, chlorobenzene
The yield of glycine is 99.9% or more.It is 9.0wt% by the content that obtained hydrolyzate is diluted with water to potassium ion, chlorobenzene is sweet
The content of propylhomoserin is 21.41wt%, and 866.6742g hydrolyzate is obtained after dilution.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.3MPa, in
It is 20 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 8.2, filter out solid, wash,
Drying obtains a chlorophenyl glycine product 151.5167g, and main content is 98wt%, the product be it is powdered, grasped by recrystallization
Make, obtain chlorophenyl glycine product between the DL- of lenticular, purity reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filter
Liquid is the potassium bicarbonate aqueous solution containing chlorophenyl glycine, and the quality of filtrate is 858.5740g, wherein potassium ion quality percentage
Content is 9.08wt%, and the mass percentage of chlorophenyl glycine is 4.32wt%, and the filtrate is by heating decarburization, being concentrated into potassium
Mass of ion percentage composition is recycled to lower batch glycolylurea hydrolysis, the mother liquor quality obtained after decarburization, concentration after being 28.5wt% or so
For 273.5387g.
Embodiment 6
Preparation of the DL- to fluorophenyl glycine:
By mass percentage be 90wt% 2- hydroxyl-to 167.9311 grams of fluorophenyl acetonitrile aqueous solution (cyanalcohol) (1.0 moles) with
Ammonia and carbon dioxide content are respectively 453.3333 grams of the carbon ammonium aqueous solution (cyanalcohol: ammonia: carbon dioxide of 7.5wt% and 14.56wt%
=1.0:2.0:1.5) it is pumped into micro passage reaction by metering pump simultaneously, flow velocity of the cyanalcohol in microchannel is 10.0g/
Min, flow velocity of the carbon ammonium aqueous solution in microchannel are 27.0g/min, and the temperature for controlling reaction is 120 DEG C, pressure 1.5MPa,
Residence time is the time that 3min(, that is, reaction solution flows through microchannel), the liquid of outflow is the transparent 5-(of clear, colorless to fluorobenzene
Base)-hydantoins aqueous solution (glycolylurea), by deamination and carbon dioxide, it is 582.2641 grams total to obtain glycolylurea aqueous solution, wherein
5-(p-fluorophenyl)-hydantoins content be 33.35wt%, 5-(p-fluorophenyl)-hydantoins yield be greater than 99.9%(with cyanalcohol
Meter).
By 5-(p-fluorophenyl obtained above)-hydantoins aqueous solution (glycolylurea) and mass percentage be 50wt%'s
276 grams of wet chemical (glycolylurea: potassium ion=1.0:2.0) is pumped into micro passage reaction by metering pump simultaneously, and glycolylurea is again
Flow velocity in microchannel is 58.9g/min, and flow velocity of the wet chemical in microchannel is 27.92g/min, controls reaction
Temperature is 178 DEG C, pressure 2.5MPa, and the residence time is the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow
For clear light yellow transparent liquid, which passes through deamination and carbon dioxide, obtains to fluorophenyl glycine aqueous solutions of potassium
745.2641g, wherein the mass percentage to fluorophenyl glycine is 22.70wt%, potassium ion mass percentage is
10.47wt%, the yield to fluorophenyl glycine are 99.9% or more.It is by the content that obtained hydrolyzate is diluted with water to potassium ion
8.5wt%, the content to fluorophenyl glycine is 18.43wt%, and 917.990g hydrolyzate is obtained after dilution.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.3MPa, in
It is 20 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 7.8, filter out solid, wash,
Drying is obtained to fluorophenyl glycine product 138.0841g, and main content is 98wt%, the product be it is powdered, grasped by recrystallization
Make, obtain the DL- of lenticular to fluorophenyl glycine product, purity reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filter
Liquid is containing the potassium bicarbonate aqueous solution to fluorophenyl glycine, and the quality of filtrate is 860.5740g, wherein potassium ion quality percentage
Content is 9.06wt%, and the mass percentage to fluorophenyl glycine is 3.93wt%, and the filtrate is by heating decarburization, being concentrated into potassium
Mass of ion percentage composition is recycled to lower batch glycolylurea hydrolysis after being 30wt%, the mother liquor quality obtained after decarburization, concentration is
259.9136g。
Embodiment 7
The preparation of DL- neighbour's fluorophenyl glycine:
By mass percentage be 90wt% 2- hydroxyl -167.9311 grams of neighbour fluorophenyl acetonitrile aqueous solution (cyanalcohol) (1.0 moles) and
Ammonia and carbon dioxide content are respectively 453.3333 grams of the carbon ammonium aqueous solution (cyanalcohol: ammonia: carbon dioxide of 7.5wt% and 14.56wt%
=1.0:2.0:1.5) it is pumped into micro passage reaction by metering pump simultaneously, flow velocity of the cyanalcohol in microchannel is 10.0g/
Min, flow velocity of the carbon ammonium aqueous solution in microchannel are 27.0g/min, and the temperature for controlling reaction is 120 DEG C, pressure 1.5MPa,
Residence time is the time that 3min(, that is, reaction solution flows through microchannel), the liquid of outflow is the transparent 5-(neighbour's fluorobenzene of clear, colorless
Base)-hydantoins aqueous solution (glycolylurea), by deamination and carbon dioxide, it is 582.2641 grams total to obtain glycolylurea aqueous solution, wherein
5-(o-fluorophenyl)-hydantoins content be 33.35wt%, 5-(o-fluorophenyl)-hydantoins yield be greater than 99.9%(with cyanalcohol
Meter).
By 5-(o-fluorophenyl obtained above)-hydantoins aqueous solution (glycolylurea) and mass percentage be 50wt%'s
276 grams of wet chemical (glycolylurea: potassium ion=1.0:2.0) is pumped into micro passage reaction by metering pump simultaneously, and glycolylurea is again
Flow velocity in microchannel is 58.9g/min, and flow velocity of the wet chemical in microchannel is 27.92g/min, controls reaction
Temperature is 178 DEG C, pressure 2.5MPa, and the residence time is the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow
For clear light yellow transparent liquid, which passes through deamination and carbon dioxide, obtains adjacent fluorophenyl glycine aqueous solutions of potassium
745.2641g, wherein the mass percentage of adjacent fluorophenyl glycine is 22.70wt%, potassium ion mass percentage is
10.47wt%, the yield of adjacent fluorophenyl glycine are 99.9% or more.It is by the content that obtained hydrolyzate is diluted with water to potassium ion
The content of 8.5wt%, adjacent fluorophenyl glycine are 18.43wt%, and 917.990g hydrolyzate is obtained after dilution.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.3MPa, in
It is 20 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 7.8, filter out solid, wash,
Drying obtains adjacent fluorophenyl glycine product 138.0841g, and main content is 98wt%, the product be it is powdered, grasped by recrystallization
Make, obtain DL- neighbour's fluorophenyl glycine product of lenticular, purity reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filter
Liquid is the potassium bicarbonate aqueous solution containing adjacent fluorophenyl glycine, and the quality of filtrate is 860.5740g, wherein potassium ion quality percentage
Content is 9.06wt%, and the mass percentage of adjacent fluorophenyl glycine is 3.93wt%, and the filtrate is by heating decarburization, being concentrated into potassium
Mass of ion percentage composition is recycled to lower batch glycolylurea hydrolysis after being 30wt%, the mother liquor quality obtained after decarburization, concentration is
259.9136g。
Embodiment 8
The preparation of fluorophenyl glycine between DL-:
By mass percentage be 70wt% 215.9114 grams of 2- hydroxyl-fluorophenyl acetonitrile aqueous solution (cyanalcohol) (1.0 moles) with
Ammonia and carbon dioxide content are respectively 453.3333 grams of the carbon ammonium aqueous solution (cyanalcohol: ammonia: carbon dioxide of 7.5wt% and 14.56wt%
=1.0:2.0:1.5) it is pumped into micro passage reaction by metering pump simultaneously, flow velocity of the cyanalcohol in microchannel is 10.0g/
Min, flow velocity of the carbon ammonium aqueous solution in microchannel are 21.0g/min, and the temperature for controlling reaction is 110 DEG C, pressure 1.3MPa,
Residence time is the time that 6min(, that is, reaction solution flows through microchannel), the liquid of outflow is fluorobenzene between the transparent 5-(of clear, colorless
Base)-hydantoins aqueous solution (glycolylurea), by deamination and carbon dioxide, it is 630.2447 grams total to obtain glycolylurea aqueous solution, wherein
Fluorophenyl between 5-()-hydantoins content is 30.81wt%, fluorophenyl between 5-()-hydantoins yield is greater than 99.9%(with cyanalcohol
Meter).
By fluorophenyl between 5-(obtained above)-hydantoins aqueous solution (glycolylurea) and mass percentage be 50wt%'s
276 grams of wet chemical (glycolylurea: potassium ion=1.0:2.0) is pumped into micro passage reaction by metering pump simultaneously, and glycolylurea is again
Flow velocity in microchannel is 58.9g/min, and flow velocity of the wet chemical in microchannel is 25.79g/min, controls reaction
Temperature is 168 DEG C, pressure 2.0MPa, and the residence time is the time that 4min(, that is, reaction solution flows through microchannel), the liquid of outflow
For clear light yellow transparent liquid, which passes through deamination and carbon dioxide, obtains a fluorophenyl glycine aqueous solutions of potassium
The mass percentage of 845.2447g, in-between fluorophenyl glycine are 20.01wt%, and potassium ion mass percentage is
9.23wt%, the yield of fluorophenyl glycine are 99.9% or more.
Hydrolyzate obtained above is passed through carbon dioxide gas, the pressure for being passed through carbon dioxide gas is 0.3MPa, in
It is 20 DEG C, mixing speed 120r/min with temperature, is passed through in carbon dioxide and terminal pH is 7.8, filter out solid, wash,
Drying obtains a fluorophenyl glycine product 138.0841g, and main content is 98wt%, the product be it is powdered, grasped by recrystallization
Make, obtain DL- neighbour's fluorophenyl glycine product of lenticular, purity reaches 99.5wt% or more, and recrystallization mother liquor is recycled.Filter
Liquid is the potassium bicarbonate aqueous solution containing adjacent fluorophenyl glycine, and the quality of filtrate is 760.5740g, wherein potassium ion quality percentage
Content is 10.26wt%, and the mass percentage of fluorophenyl glycine is 4.45wt%, and the filtrate is by heating decarburization, being concentrated into
Potassium ion mass percentage is recycled to lower batch glycolylurea hydrolysis after being 30wt%, the mother liquor quality obtained after decarburization, concentration is
260.1142g, the mass percentage of in-between fluorophenyl glycine are 13.0wt%.
In conclusion the present invention use micro passage reaction, greatly shorten glycolylurea preparation and the alkaline hydrolysis time, acceleration react into
Row reduces cyanalcohol pyrolysis polymerization, and no coupling product generates and brine waste generates, and product yield is high, and clean and environmental protection reduces life
Produce cost.Above-described embodiment with (50 μm -300 μm) of German IMM micro passage reaction be experiment porch, microreactor mass-and heat-transfer
Speed is fast, therefore, when 2- hydroxy-benzyl cyanide and the like and carbon ammonium aqueous solution pass through micro passage reaction, mass transfer, heat transfer effect
Fruit is obvious, and making it, intermolecular collision in cyclization process increases, storeroom mixing is full and uniform, heat transfer is abundant, increases
The pressure of reaction promotes reaction to carry out to product direction, shortens the cyclisation time, effectively reduces 2- hydroxy-benzyl cyanide and its similar
Object pyrolysis polymerization and by-product generate；Accelerate cyclization and hydrolysis reaction, makes 2- hydroxy-benzyl cyanide and the like most
It is converted into bigization glycolylurea, the thorough hydrolysis of glycolylurea is phenylglycine and the like, is hydrolyzed using potassium carbonate, and carbonic acid
Potassium Recycling Mother Solution is applied, and no coupling product generates and brine waste generates, and product yield is high, and clean and environmental protection reduces production cost.
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of continuously quickly prepare DL- phenylglycine and its similar method, it is characterised in that: include: by 2- hydroxyl-benzene second
Nitrile and the like is added micro passage reaction with carbon ammonium aqueous solution and is reacted, and control reaction temperature is 80~130 DEG C, pressure
For 0.5~2.0MPa, reactant residence time in microchannel is 1~8min, obtains 5- phenyl-hydantoins and the like
Aqueous solution；Micro passage reaction is added with alkali in glycolylurea to react, control reaction temperature is 120~200 DEG C, pressure 1.0
~3.5MPa, residence time of the reactant in microchannel are 1~8min, obtain phenylglycine and the like saline solution,
Acidified neutralization, crystallization obtain DL- phenylglycine and the like；The 2- hydroxy-benzyl cyanide and the like abbreviation cyanogen
Alcohol, described 5- phenyl-hydantoins and the like abbreviation glycolylurea.
2. according to the method described in claim 1, it is characterized by: described 2- hydroxy-benzyl cyanide and the like, 5- benzene
Its general formula of the chemical structure of base-hydantoins and the like and DL- phenylglycine and the like is as follows:
In formula R group be phenyl ring on ortho position, meta or para position, R group be one of hydrogen atom, chlorine atom, fluorine atom or
Person is a variety of；Described 2- hydroxy-benzyl cyanide and the like be liquid or solid-state, mass percentage be 70wt%~
99wt%, in described 5- phenyl-hydantoins and the like aqueous solution, the quality of 5- phenyl-hydantoins and the like
Percentage composition is 10wt%~50wt%, in described phenylglycine and the like saline solution, phenylglycine and the like
Mass percentage is 10wt%~40wt%.
3. according to the method described in claim 1, it is characterized by: described 2- hydroxy-benzyl cyanide and the like and ammonium bicarbonate water
Solution molar ratio are as follows: cyanalcohol/ammonia/carbon dioxide=1:1.5~2.0:1.0~1.5, control reaction temperature are 100~130
DEG C, pressure is 0.5~1.5MPa, and reactant residence time in microchannel is 2~5min, in carbon ammonium aqueous solution, the quality of ammonia
Percentage composition is 5wt%~10wt%, and the mass percentage of carbon dioxide is 8wt%~19.5wt%.
4. according to the method described in claim 1, it is characterized by: the alkali is selected from sodium hydroxide, potassium hydroxide, hydroxide
At least one of calcium, barium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus, particularly preferred wet chemical, matter
Amount percentage composition is 30wt%~55wt%.
5. method according to claim 1 or 4, it is characterised in that: described 5- phenyl-hydantoins and the like and carbon
The molar ratio of sour potassium are as follows: glycolylurea/potassium ion=1:1.2~2.5, control reaction temperature are 160~180 DEG C, pressure 1.5
~2.5MPa, residence time of the reactant in microchannel are 2~8min.
6. according to the method described in claim 1, it is characterized by: the acidulant be selected from sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid,
At least one of carbonic acid, carbon dioxide.
7. method according to claim 1 or 6, it is characterised in that: described phenylglycine and the like sylvite aqueous solution
In, ammonia content is lower than 50ppm, and the mass percentage of potassium ion is 6.0wt%~11.5wt%.
8. according to the method described in claim 1, it is characterized by: the acidizing crystal mother liquor is to contain phenylglycine and its class
In potassium bicarbonate aqueous solution like object, the mass percentage of phenylglycine and the like is 2wt%~10wt%, saleratus
Mass percentage be 10wt%~25wt%, the mother liquor by heating decarburization, obtain after concentration potassium carbonate and phenylglycine and
The mixed aqueous solution of its analog sylvite is recycled to 5- phenyl-hydantoins and the like hydrolysis, after concentration, potassium in mother liquor
Mass of ion percentage composition is not less than 20wt%.
9. method according to claim 1 or 8, it is characterised in that: the potassium ion with (5- phenyl-hydantoins and its
Analog+phenylglycine and the like) molar ratio be 1.2~2.5:1.0, control reaction temperature be 160~180
DEG C, pressure is 1.5~2.5MPa, and residence time of the reactant in microchannel is 2~8min.
10. any one the method according to claim 1~9, which is characterized in that the sweet ammonia of DL- benzene according to made from the above method
Acid and the like, described DL- phenylglycine and the like are selected from DL- phenylglycine, DL- o-chlorobenzene glycine, DL- m-chloro
Phenylglycine, DL- p-chlorophenylglycine, DL- between fluorophenyl glycine, DL- o fluorobenzaldehyde, DL- in fluorophenyl glycine extremely
Few one kind.
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| CN106083628A (en) * | 2016-06-01 | 2016-11-09 | 河北诚信有限责任公司 | A kind of method preparing p-chlorophenylglycine |
| CN106380415A (en) * | 2016-08-29 | 2017-02-08 | 宁夏紫光天化蛋氨酸有限责任公司 | Preparation method for D, L-phenylglycine and analogue thereof |
| CN106518660A (en) * | 2016-09-28 | 2017-03-22 | 浙江新和成股份有限公司 | Preparation method of alpha-ketoleucine calcium dihydrate or alpha-ketophenylalanine calcium monohydrate |
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| CN106083628A (en) * | 2016-06-01 | 2016-11-09 | 河北诚信有限责任公司 | A kind of method preparing p-chlorophenylglycine |
| CN106380415A (en) * | 2016-08-29 | 2017-02-08 | 宁夏紫光天化蛋氨酸有限责任公司 | Preparation method for D, L-phenylglycine and analogue thereof |
| CN106518660A (en) * | 2016-09-28 | 2017-03-22 | 浙江新和成股份有限公司 | Preparation method of alpha-ketoleucine calcium dihydrate or alpha-ketophenylalanine calcium monohydrate |
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| CN112574049A (en) * | 2020-12-17 | 2021-03-30 | 华阳新材料科技集团有限公司 | Novel method for preparing phenylglycine by using hydrocyanic acid |
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