CN107011299A - A kind of method that SMIA is reclaimed in the waste liquid from SMIA - Google Patents
A kind of method that SMIA is reclaimed in the waste liquid from SMIA Download PDFInfo
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- CN107011299A CN107011299A CN201710183227.8A CN201710183227A CN107011299A CN 107011299 A CN107011299 A CN 107011299A CN 201710183227 A CN201710183227 A CN 201710183227A CN 107011299 A CN107011299 A CN 107011299A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
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Abstract
The invention provides a kind of method that SMIA is reclaimed in waste liquid from SMIA, including：SMIA dreg liquid reacts under conditions of solvent, catalyst, obtains SMIA；One or more of the catalyst in metal chlorination salt, metal sulfate, metal nitrate, hydrophosphate, metal oxide, inorganic acid, organic acid and inorganic base；One or more of the metal in sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt；The reaction temperature is 50~150 DEG C.The present invention reacts SMIA dreg liquid under specific catalyst system, specified temp and solvent existence condition, it is (Z) formula SMIA by the directly upset of (E) formula SMIA to realize one-step method, finally gives thermodynamically stable SMIA product.The inventive method step is simple, recovery yield that is economic and environment-friendly and being effectively improved SMIA, it is adaptable to industrialized production, while reducing the environmental protection pressure of SMIA waste liquid.
Description
Technical field
The present invention relates to technical field of medical intermediate preparation, furan is reclaimed from SMIA waste liquid more particularly, to one kind
Mutter the method for ammonium salt.
Background technology
Cis SMIA is the key intermediate for synthesizing broad-spectrum antibiotic CEFUROXIME AXETIL (sodium), with domestic and international market
CEFUROXIME AXETIL (sodium) demand is increased sharply, the market demand of cis SMIA is also substantially improved.However, in existing system
In the technical process of standby cis SMIA, during due to oximate in the industrial production, there is cis-trans isomerization, inevitably
The organic waste residues liquid of trans SMIA isomers can be produced.This not only serious waste chemical raw material, the energy, human resources,
Production efficiency and economic benefit are reduced, and there is in subsequent treatment environmental pollution and potential safety hazard, and produces great number and is given up
Slag liquid processing cost.
Up to the present, prior art prepares the research of cis SMIA on being reclaimed from SMIA dreg liquid,
The method of report is mostly following two.The A of Chinese patent CN 102070572 disclose one kind under the conditions of acid medium, utilize
Sodium nitrite solution reclaims furans ketone acid from SMIA waste liquid, then undergoes with the oximation reaction of methoxamine, ammonification into salt system
Standby SMIA.Although this method can obtain SMIA, there are problems：Carried out first using natrium nitrosum
During oxidation prepares furans ketone acid, the waste gas of the severe contamination environment such as substantial amounts of nitric oxide and nitrogen dioxide can be produced；
Secondly, further by keto acid transformation for the oximate of SMIA during, it is necessary to be continuing with expensive methoxamine, and
And in this course, still inevitably result from trans SMIA；Complex technical process, yield is low, adds back
The cost for skill of knocking off.The A of Chinese patent CN 103554069 disclose a kind of using photoisomerization principle, by selecting 254-
540nm ultraviolet light, by method of the trans byproduct upset in SMIA dreg liquid for cis product.Though this method
The yield so overturn is higher, and process is fairly simple, but needs to use mesohigh mercury lamp and actinic reactor, and reaction temperature is difficult
Control；Furthermore, it is necessary to add substantial amounts of solvent into reactor, cost is added, this just constrains it in industrial production
Using exploitation was a kind of both cheap, environmentally friendly, simple to operate, and the synthetic route for being applied to industrialized production again, which is that strategic point is to be solved, asks
Topic.
The content of the invention
In view of this, the technical problem to be solved in the present invention is that provide one kind reclaims furans ammonium from SMIA waste liquid
The method of salt, recovery method of the invention is simple and environmentally-friendly, high income.
The invention provides a kind of method that SMIA is reclaimed in waste liquid from SMIA, including：
SMIA dreg liquid reacts under conditions of solvent, catalyst, obtains SMIA；
The catalyst is selected from metal chlorination salt, metal sulfate, metal nitrate, hydrophosphate, metal oxide, nothing
One or more in machine acid, organic acid and inorganic base；The metal in sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt one
Plant or several；
The reaction temperature is 50~150 DEG C.
It is preferred that, the catalyst is selected from metal chlorination salt, metal sulfate, metal nitrate, hydrophosphate, metal oxygen
Two or more in compound, organic acid and inorganic base；The metal is in sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt
One or more.
It is preferred that, the catalyst is selected from calcium chloride, magnesium chloride, magnesium sulfate, magnesium nitrate, disodium hydrogen phosphate, biphosphate
Sodium, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, aluminium chloride, alundum (Al2O3), zinc chloride, zinc sulfate, chlorine
Change the one or more in iron, ferric sulfate, cobalt chloride, formic acid, ammoniacal liquor and acetic acid.
It is preferred that, the catalyst is in iron chloride, ferric sulfate, zinc sulfate, formic acid, acetic acid, ammoniacal liquor and magnesium sulfate
It is one or more of.
It is preferred that, the solvent is selected from ethers, hydro carbons, alcohols, esters, alkyl halide hydro carbons, amide-type, ketone, sulfoxide type
With the one or more in water.
It is preferred that, the solvent is selected from tetrahydrofuran, dioxane, morpholine, hexamethylene, benzene, toluene, methanol, ethanol, different
Propyl alcohol, ethyl acetate, butyl acetate, 1,2- dichloroethanes, chloroform, DMF, dimethyl sulfoxide (DMSO), N- methyl pyrroles
One or more in pyrrolidone, acetone and water.
It is preferred that, the solvent is selected from methanol, ethanol, isopropanol, DMF, dimethyl sulfoxide (DMSO), N- first
One or more in base pyrrolidones, dioxane, toluene, tetrahydrofuran, acetone and water.
It is preferred that, the reaction temperature is 80~120 DEG C；The reaction time is 2~12h.
It is preferred that, the mol ratio of the SMIA waste liquid and catalyst is 1：(0.01~0.2).
It is preferred that, the mass ratio of the SMIA waste liquid and solvent is 1：(1~5).
Compared with prior art, the invention provides a kind of method that SMIA is reclaimed in waste liquid from SMIA, bag
Include：SMIA dreg liquid reacts under conditions of solvent, catalyst, obtains SMIA；The catalyst is selected from metal chlorine
One kind in salt dissolving, metal sulfate, metal nitrate, hydrophosphate, metal oxide, inorganic acid, organic acid and inorganic base
Or it is several；One or more of the metal in sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt；The reaction temperature be 50~
150℃.The present invention reacts SMIA dreg liquid under specific catalyst system, specified temp and solvent existence condition,
It is (Z)-formula SMIA by the directly upset of (E)-formula SMIA to realize one-step method, finally gives thermodynamically stable furans ammonium
Product salt.The inventive method step is simple, recovery yield that is economic and environment-friendly and effectively raising SMIA, it is adaptable to work
Industry metaplasia is produced.The environmental protection pressure of SMIA waste liquid is reduced simultaneously.
Brief description of the drawings
Fig. 1 is the high-efficient liquid phase chromatogram of SMIA；
Fig. 2 is SMIA nuclear magnetic spectrogram.
Embodiment
The invention provides a kind of method that SMIA is reclaimed in waste liquid from SMIA, including：
SMIA dreg liquid reacts under conditions of solvent, catalyst, obtains SMIA；
The catalyst is selected from metal chlorination salt, metal sulfate, metal nitrate, hydrophosphate, metal oxide, nothing
One or more in machine acid, organic acid and inorganic base；The metal in sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt one
Plant or several；
The reaction temperature is 50~150 DEG C.
The method that SMIA is reclaimed from SMIA waste liquid that the present invention is provided is applied to SMIA waste liquid.This hair
It is bright for the SMIA waste liquid without limit, it is well known to those skilled in the art.Can be known in the art
The technical process for preparing cis SMIA in, the organic liquid waste containing trans SMIA isomers of generation.
The cis SMIA that SMIA of the present invention is known to the skilled person, chemical name is (Z) -2-
Methoxyimino -2- (furans -2- bases) ammonium acetate, shown in structure such as formula (I), trans SMIA of the present invention is (E) -2-
Methoxyimino -2- (furans -2- bases) ammonium acetate, shown in structure such as formula (II),
According to the present invention, SMIA dreg liquid reacts under conditions of solvent, catalyst, obtains SMIA.It is preferred that
Specially：SMIA dreg liquid dissolves in a solvent, the heating response under conditions of catalyst, obtains SMIA.
The heating is preferably agitating and heating, and the temperature of the heating is 50~150 DEG C；Preferably 80~120 DEG C；It is more excellent
Elect 80~110 DEG C as；The heat time is preferably 2~12h；Preferably 6~10h.
The above-mentioned specific heating-up temperature of present invention selection, be more beneficial for one-step method is by the directly upset of (E)-formula SMIA
(Z)-formula SMIA, finally gives thermodynamically stable SMIA product.
In the present invention, catalyst is selected from metal chlorination salt, metal sulfate, metal nitrate, hydrophosphate, metal oxygen
One or more in compound, inorganic acid, organic acid and inorganic base；The metal is selected from sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt
In one or more；The catalyst is preferably selected from metal chlorination salt, metal sulfate, metal nitrate, hydrophosphate, gold
Belong to two or more in oxide, organic acid and inorganic base；Wherein, the metal be selected from sodium, potassium, calcium, magnesium, aluminium, zinc,
One or more in iron and cobalt.
Wherein, the metal chlorination salt is preferably calcium chloride, magnesium chloride, aluminium chloride, zinc chloride, iron chloride or cobalt chloride；
The metal sulfate is preferably magnesium sulfate, zinc sulfate or ferric sulfate；The metal nitrate be preferably magnesium nitrate, zinc nitrate or
Ferric nitrate；The hydrophosphate is preferably disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate or potassium dihydrogen phosphate；The gold
It is preferably alundum (Al2O3) to belong to oxide；The inorganic acid is preferably hydrochloric acid, sulfuric acid or nitric acid；The organic acid is preferably acetic acid
Or formic acid；The inorganic base is preferably ammoniacal liquor；
In the present invention, the catalyst is more preferably selected from calcium chloride, magnesium chloride, magnesium sulfate, magnesium nitrate, phosphoric acid hydrogen two
Sodium, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, dibastic sodium phosphate, potassium hydrogen phosphate, aluminium chloride, alundum (Al2O3), chlorination
One or more in zinc, zinc sulfate, iron chloride, ferric sulfate, cobalt chloride, formic acid, ammoniacal liquor and acetic acid.Most preferably it is selected from chlorination
One or more in iron, ferric sulfate, zinc sulfate, formic acid, acetic acid, ammoniacal liquor and magnesium sulfate.
Wherein, catalyst is preferably the acid above-mentioned substances of Lewis；Catalyst can be thing acid above-mentioned strong Lewis
Matter；Or the cooperation of two kinds of components；Can be the mixed of dibasic alkaliine and dihydric phosphate in wherein a part of embodiment
Close；Can be the mixing of magnesium sulfate and magnesium nitrate, the present invention is to specific proportioning without limit in wherein a part of embodiment
It is fixed.
The present invention for said components specific source and preparation method without limit, it is preferably commercially available.
In the present invention, the solvent is preferably selected from ethers, hydro carbons, alcohols, esters, alkyl halide hydro carbons, amide-type, ketone
One or more in class, sulfoxide type and water.
Wherein, the ethers is preferably the one or more in tetrahydrofuran, dioxane and morpholine；The hydro carbons is preferred
For C2~C10 hydro carbons；One or more more preferably in hexamethylene, benzene and toluene；The alcohols is preferably selected from methanol, second
One or more in alcohol and isopropanol；The esters are preferably ethyl acetate or butyl acetate；The halogenated alkane is preferably
1,2- dichloroethanes or chloroform；The acid amides is preferably N,N-dimethylformamide；The ketone is preferably N- crassitudes
Ketone or acetone；The sulfoxide type is preferably dimethyl sulfoxide (DMSO).
In the present invention, the solvent is more preferably selected from tetrahydrofuran, dioxane, morpholine, hexamethylene, benzene, toluene, first
Alcohol, ethanol, isopropanol, ethyl acetate, butyl acetate, 1,2- dichloroethanes, chloroform, DMF, dimethyl are sub-
One or more in sulfone, 1-METHYLPYRROLIDONE, acetone and water.The solvent be most preferably selected from methanol, ethanol, isopropanol,
In N,N-dimethylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, dioxane, toluene, tetrahydrofuran, acetone and water
One or more.
The present invention for said components specific source and preparation method without limit, it is preferably commercially available.
The present invention coordinates specific reaction temperature to be more beneficial for one-step method under conditions of above-mentioned special catalyst and solvent
It is (Z)-formula SMIA that (E)-formula SMIA, which is directly overturn, finally gives thermodynamically stable SMIA product.Instead
Catalyst is non-toxic catalyst during answering, and without remaining additive and poisonous actual environmental protection；While this hair
It is bright to overcome the shortcoming that existing photochemical reaction is not easy amplification, it is different by the thermodynamic stability of compound, using upper
Specific condition is stated, conversion obtains (Z)-formula SMIA；Obtained product yield and purity is high.The SMIA of the present invention gives up
Liquid is handled without remaining, can devil liquor recovery utilization using the method for the present invention.
In the present invention, the mol ratio of the SMIA waste liquid and catalyst is preferably 1：(0.01~0.2)；More preferably
For 1：(0.01~0.15)；Most preferably 1：(0.01~0.05).
In the present invention, the mass ratio of the SMIA waste liquid and solvent is preferably 1：(1~5)；More preferably 1：(1
~4)；Most preferably 1：(1~2).
Reaction solution is obtained after reaction；Reaction solution of the present invention is carried using the mode that isolates and purifies of existing conventional SMIA
Pure, the present invention is to this and is not limited, well known to those skilled in the art.
The invention provides a kind of method that SMIA is reclaimed in waste liquid from SMIA, including：SMIA waste residue
Liquid reacts under conditions of solvent, catalyst, obtains SMIA；The catalyst be selected from metal chlorination salt, metal sulfate,
One or more in metal nitrate, hydrophosphate, metal oxide, inorganic acid, organic acid and inorganic base；The metal choosing
One or more from sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt；The reaction temperature is 50~150 DEG C.The present invention is by furans
Ammonium salt dreg liquid reacts under specific catalyst system, specified temp and solvent existence condition, realizes one-step method by (E)-formula
It is (Z)-formula SMIA that SMIA, which is directly overturn, finally gives thermodynamically stable SMIA product.The inventive method
Step is simple, recovery yield that is economic and environment-friendly and being effectively improved SMIA, it is adaptable to industrialized production.Reduce simultaneously
The environmental protection pressure of SMIA waste liquid.
The present invention is preferably carried out by reverse high performance liquid chromatography to the purity of SMIA and conversion ratio that prepare
Determine.Design parameter is：
Chromatographic column：Hypersil BDS C18 250mm×0.46mm 5μm；
Mobile phase:PH=3.0 phosphate (takes potassium dihydrogen phosphate 2.72g, is dissolved in water and is diluted to 1000mL, shake up, use
The pH value of 80% (V/V) phosphorus acid-conditioning solution is 3.0 ± 0.1)-acetonitrile (100：8) it is mobile phase.
Flow velocity：1.0mL/min；
Detector：UV-detector, wavelength：255n；
Sample size：20uL.
In order to further illustrate the present invention, the present invention is provided with reference to embodiments reclaims from SMIA waste liquid
The method of SMIA is described in detail.
Embodiment 1
Weigh 500g SMIA dreg liquids (Z/E=1:7) dilution of 1000mL ethanol, is added, while adding 25g tri-chlorinations
Iron, stirs and is warming up to 80 DEG C, and heating stirring stops heating after 6 hours, the reaction solution that reaction is obtained after terminating is according to the present invention
Described method detects that Z/E=63/37, reaction solution is purified using existing isolation and purification method, can be obtained through HPLC
265g SMIA products, are computed yield 53%, and product detects purity >=99.6%, and trans-isomer content through HPLC
≤ 0.10%, product is white solid, and indices all comply fully with industrial production demand.
As depicted in figs. 1 and 2, Fig. 1 is the high-efficient liquid phase chromatogram of SMIA to measurement result；It can be drawn by Fig. 1：
Fig. 2 is SMIA nuclear magnetic spectrogram,1H NMR(300MHz,CD3OD)δ7.59(s,1H),6.57(s,1H),6.52
(s, 1H), 4.95 (s, 4H), 3.89 (s, 3H), can be defined as the structure of SMIA by Fig. 2.
Embodiment 2
Weigh 500g SMIA dreg liquids (Z/E=1:7) 1000mL DMF dilutions, are added, while adding 5% vinegar
Acid, stirs and is warming up to 90 DEG C, and heating stirring stops heating after 6 hours, the reaction solution that reaction is obtained after terminating is according to the present invention
Described is detected through HPLC, and Z/E=59/41 is purified using existing isolation and purification method, can obtain 257g furans ammoniums
Product salt, is computed yield 51%, and product detects purity >=99.5%, and trans-isomer content≤0.10% through HPLC,
Product is white solid, and the light transmittance and turbidity of product all comply fully with industrial production demand.
Embodiment 3
Weigh 500g SMIA dreg liquids (Z/E=1:7) 1200mL DMF dilutions, are added, while adding 25g tri-chlorinations
Iron, stirs and is warming up to 90 DEG C, and heating stirring stops heating after 8 hours, the reaction solution that reaction is obtained after terminating is according to the present invention
Described method detects that Z/E=69/31, reaction solution is purified using existing isolation and purification method, can be obtained through HPLC
260g SMIA products, are computed yield 52%, and product detects purity >=99.6%, and trans-isomer content through HPLC
≤ 0.10%, product is white solid, and indices all comply fully with industrial production demand.
Embodiment 4
Weigh 500g SMIA dreg liquids (Z/E=1:7) 1000mL methanol dilutions, are added, while adding 25g sulfuric acid
Zinc, stirs and is warming up to 85 DEG C, and heating stirring stops heating after 7.5 hours, the reaction solution that reaction is obtained after terminating is according to this hair
Bright described method detects that Z/E=68/32, reaction solution is purified using existing isolation and purification method, can be obtained through HPLC
To 255g SMIA products, yield 51% is computed, product detects purity >=99.6% through HPLC, and transisomer contains
Amount≤0.10%, product is white solid, and indices all comply fully with industrial production demand.
Embodiment 5
Weigh 500g SMIA dreg liquids (Z/E=1:7) dilution of 1000mL dimethyl sulfoxide (DMSO)s, is added, is added simultaneously
9.5g acetic acid, stirs and is warming up to 110 DEG C, and heating stirring stops heating after 8 hours, the reaction solution that reaction is obtained after terminating according to
Method of the present invention detects that Z/E=72/28, reaction solution is purified using existing isolation and purification method, can through HPLC
To obtain 265g SMIA products, yield 53% is computed, product detects purity >=99.6%, and trans-isomerism through HPLC
Body content≤0.10%, product is white solid, and indices all comply fully with industrial production demand.
Embodiment 6
Weigh 500g SMIA dreg liquids (Z/E=1:7) dilution of 1200mL dioxane, is added, while adding 8.0g
Ammoniacal liquor, stirs and is warming up to 95 DEG C, and heating stirring stops heating after 10 hours, the reaction solution that reaction is obtained after terminating is according to this hair
Bright described method detects that Z/E=62/38, reaction solution is purified using existing isolation and purification method, can be obtained through HPLC
To 230g SMIA products, yield 46% is computed, product detects purity >=99.6% through HPLC, and transisomer contains
Amount≤0.10%, product is white solid, and indices all comply fully with industrial production demand.
Embodiment 7
Weigh 500g SMIA dreg liquids (Z/E=1:7) 1000mL dilution with toluene, is added, while adding 18.6g sulfuric acid
Magnesium, stirs and is warming up to 120 DEG C, and heating stirring stops heating after 7 hours, the reaction solution that reaction is obtained after terminating is according to the present invention
Described method detects that Z/E=68/32, reaction solution is purified using existing isolation and purification method, can be obtained through HPLC
240g SMIA products, are computed yield 48%, and product detects purity >=99.6%, and trans-isomer content through HPLC
≤ 0.10%, product is white solid, and indices all comply fully with industrial production demand.
Embodiment 8
Weigh 500g SMIA dreg liquids (Z/E=1:7) aqueous solution (THF of 1000mL tetrahydrofurans, is added:H2O=
1:1) dilute, while adding 20g cobalt chlorides, stir and be warming up to 100 DEG C, heating stirring stops heating after 9 hours, and reaction terminates
The reaction solution obtained afterwards detects that Z/E=59/41, reaction solution uses existing separation through HPLC according to the method described in the present invention
Purification process is purified, and can obtain 195g SMIA products, is computed yield 39%, product through HPLC detect purity >=
99.6%, and trans-isomer content≤0.10%, product is white solid, and indices all comply fully with industrial production and needed
Ask.
Embodiment 9
Weigh 500g SMIA dreg liquids (Z/E=1:7) dilution of 1000mL ethanol, is added, while adding 5.3g phosphoric acid
Disodium hydrogen and 7.5g sodium dihydrogen phosphates, stir and are warming up to 95 DEG C, and heating stirring stops heating after 6 hours, reaction terminate after
To reaction solution detect that Z/E=63/37, reaction solution is isolated and purified using existing through HPLC according to the method described in the present invention
Method is purified, and can obtain 265g SMIA products, is computed yield 53%, product through HPLC detect purity >=
99.6%, and trans-isomer content≤0.10%, product is white solid, and indices all comply fully with industrial production and needed
Ask.
Embodiment 10
Weigh 500g SMIA dreg liquids (Z/E=1:7) dilution of 1000mL ethanol, is added, while adding 13g zinc chloride
With 10g zinc sulfate, stir and be warming up to 98 DEG C, heating stirring stops heating after 6 hours, the reaction solution that reaction is obtained after terminating by
Detected according to method of the present invention through HPLC, Z/E=69/31, reaction solution is purified using existing isolation and purification method,
260g SMIA products can be obtained, yield 52% is computed, product detects purity >=99.6% through HPLC, and trans different
Structure body content≤0.10%, product is white solid, and indices all comply fully with industrial production demand.
Comparative example 1
Weigh 500g SMIA dreg liquids (Z/E=1:7) dilution of 1000mL water, is added, stirs and is warming up to 120 DEG C,
Heating stirring stops heating after 10 hours, the reaction solution that reaction is obtained after terminating is examined through HPLC according to the method described in the present invention
Survey, Z/E=40/60, reaction solution is purified using existing isolation and purification method, can obtain 115g SMIA products,
Yield 23% is computed, product detects purity >=99.6%, and trans-isomer content≤0.10% through HPLC, and product is white
Color solid, indices all comply fully with industrial production demand.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. the method for SMIA is reclaimed in a kind of waste liquid from SMIA, it is characterised in that including：
SMIA dreg liquid reacts under conditions of solvent, catalyst, obtains SMIA；
The catalyst is selected from metal chlorination salt, metal sulfate, metal nitrate, hydrophosphate, metal oxide, inorganic
One or more in acid, organic acid and inorganic base；The one kind of the metal in sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt
Or it is several；
The reaction temperature is 50~150 DEG C.
2. the method according to claim 1 for reclaiming SMIA, it is characterised in that the catalyst is selected from metal chlorination
Two kinds or two kinds in salt, metal sulfate, metal nitrate, hydrophosphate, metal oxide, organic acid and inorganic base with
On；One or more of the metal in sodium, potassium, calcium, magnesium, aluminium, zinc, iron and cobalt.
3. it is according to claim 1 reclaim SMIA method, it is characterised in that the catalyst be selected from calcium chloride,
Magnesium chloride, magnesium sulfate, magnesium nitrate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, dibastic sodium phosphate, phosphorus
In potassium hydrogen phthalate, aluminium chloride, alundum (Al2O3), zinc chloride, zinc sulfate, iron chloride, ferric sulfate, cobalt chloride, formic acid, ammoniacal liquor and acetic acid
One or more.
4. it is according to claim 3 reclaim SMIA method, it is characterised in that the catalyst be selected from iron chloride,
One or more in ferric sulfate, zinc sulfate, formic acid, acetic acid, ammoniacal liquor and magnesium sulfate.
5. it is according to claim 1 reclaim SMIA method, it is characterised in that the solvent be selected from ethers, hydro carbons,
One or more in alcohols, esters, alkyl halide hydro carbons, amide-type, ketone, sulfoxide type and water.
6. it is according to claim 5 reclaim SMIA method, it is characterised in that the solvent be selected from tetrahydrofuran,
Dioxane, morpholine, hexamethylene, benzene, toluene, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, 1,2- dichloroethanes,
One or more in chloroform, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, acetone and water.
7. it is according to claim 6 reclaim SMIA method, it is characterised in that the solvent be selected from methanol, ethanol,
Isopropanol, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), 1-METHYLPYRROLIDONE, dioxane, toluene, tetrahydrofuran, acetone
With the one or more in water.
8. the method according to claim 1 for reclaiming SMIA, it is characterised in that the reaction temperature is 80~120
℃；The reaction time is 2~12h.
9. the method according to claim 1 for reclaiming SMIA, it is characterised in that the SMIA waste liquid and catalysis
The mol ratio of agent is 1：(0.01~0.2).
10. the method according to claim 1 for reclaiming SMIA, it is characterised in that the SMIA waste liquid and molten
The mass ratio of agent is 1：(1~5).
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| CN109942598A (en) * | 2019-04-17 | 2019-06-28 | 广东立国制药有限公司 | A kind of preparation method of trans- cefuroxime derivative |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102070572A (en) * | 2010-12-17 | 2011-05-25 | 山东金城医药化工股份有限公司 | Method for recovering and preparing furanone acid from syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue |
| CN103554069A (en) * | 2013-11-20 | 2014-02-05 | 山东金城医药化工股份有限公司 | Method for recovering furan ammonium salt from furan ammonium salt waste residue |
| CN105254603A (en) * | 2015-10-12 | 2016-01-20 | 山东金城医药化工股份有限公司 | Synthetic technology of furan ammonium salt |
| CN105330627A (en) * | 2015-11-24 | 2016-02-17 | 辽宁大学 | Method for preparing syn-2-methoxyimino-2-(furyl-2-yl) acetic acid ammonium salt at high selectivity |
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| CN102070572A (en) * | 2010-12-17 | 2011-05-25 | 山东金城医药化工股份有限公司 | Method for recovering and preparing furanone acid from syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue |
| CN103554069A (en) * | 2013-11-20 | 2014-02-05 | 山东金城医药化工股份有限公司 | Method for recovering furan ammonium salt from furan ammonium salt waste residue |
| CN105254603A (en) * | 2015-10-12 | 2016-01-20 | 山东金城医药化工股份有限公司 | Synthetic technology of furan ammonium salt |
| CN105330627A (en) * | 2015-11-24 | 2016-02-17 | 辽宁大学 | Method for preparing syn-2-methoxyimino-2-(furyl-2-yl) acetic acid ammonium salt at high selectivity |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109942598A (en) * | 2019-04-17 | 2019-06-28 | 广东立国制药有限公司 | A kind of preparation method of trans- cefuroxime derivative |
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