CN108912019A - The method that one kind recycling mantoquita and ethyl alcohol from D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor - Google Patents
The method that one kind recycling mantoquita and ethyl alcohol from D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor Download PDFInfo
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- CN108912019A CN108912019A CN201810879167.8A CN201810879167A CN108912019A CN 108912019 A CN108912019 A CN 108912019A CN 201810879167 A CN201810879167 A CN 201810879167A CN 108912019 A CN108912019 A CN 108912019A
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- 239000012452 mother liquor Substances 0.000 title claims abstract description 69
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 58
- GKCXXDSWWDWUHS-BYPYZUCNSA-N ethyl (2s)-2-amino-3-hydroxypropanoate Chemical compound CCOC(=O)[C@@H](N)CO GKCXXDSWWDWUHS-BYPYZUCNSA-N 0.000 title claims abstract description 39
- 235000019441 ethanol Nutrition 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims description 6
- 230000032050 esterification Effects 0.000 claims abstract description 33
- 238000005886 esterification reaction Methods 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- 239000000706 filtrate Substances 0.000 claims abstract description 23
- 238000004821 distillation Methods 0.000 claims abstract description 13
- 230000007062 hydrolysis Effects 0.000 claims abstract description 11
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 11
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 6
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- 238000004321 preservation Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 8
- WAQKWTKBBXMNMA-VWMHFEHESA-N C(C)OC([C@@H](N)CO)=O.CS(=O)(=O)C1=CC=CC=C1 Chemical compound C(C)OC([C@@H](N)CO)=O.CS(=O)(=O)C1=CC=CC=C1 WAQKWTKBBXMNMA-VWMHFEHESA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000002351 wastewater Substances 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 6
- 239000000047 product Substances 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 16
- 239000007788 liquid Substances 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 8
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 8
- JCDWETOKTFWTHA-UHFFFAOYSA-N methylsulfonylbenzene Chemical compound CS(=O)(=O)C1=CC=CC=C1 JCDWETOKTFWTHA-UHFFFAOYSA-N 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- CQDKWRSVEUXESU-TYOUJGAFSA-N [Cu].N[C@@H](CO)C(=O)O.CS(=O)(=O)C1=CC=CC=C1 Chemical compound [Cu].N[C@@H](CO)C(=O)O.CS(=O)(=O)C1=CC=CC=C1 CQDKWRSVEUXESU-TYOUJGAFSA-N 0.000 description 4
- AYIRNRDRBQJXIF-NXEZZACHSA-N (-)-Florfenicol Chemical compound CS(=O)(=O)C1=CC=C([C@@H](O)[C@@H](CF)NC(=O)C(Cl)Cl)C=C1 AYIRNRDRBQJXIF-NXEZZACHSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229960003760 florfenicol Drugs 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- WIIZWVCIJKGZOK-RKDXNWHRSA-N chloramphenicol Chemical compound ClC(Cl)C(=O)N[C@H](CO)[C@H](O)C1=CC=C([N+]([O-])=O)C=C1 WIIZWVCIJKGZOK-RKDXNWHRSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 description 1
- QHBQADMYUWVKAK-VWMHFEHESA-N C(C)OC([C@@H](N)CO)=O.C1=CC=CC=C1 Chemical compound C(C)OC([C@@H](N)CO)=O.C1=CC=CC=C1 QHBQADMYUWVKAK-VWMHFEHESA-N 0.000 description 1
- 0 C*c1ccc(C(*C(O)OC([C@@](C2=C)N)[C@@]2NC(C(*)c(cc2)ccc2S(C)(=O)=O)C(OC)=O)O)cc1 Chemical compound C*c1ccc(C(*C(O)OC([C@@](C2=C)N)[C@@]2NC(C(*)c(cc2)ccc2S(C)(=O)=O)C(OC)=O)O)cc1 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FLSHWSFJJIXMDU-QRPNPIFTSA-N [Cu].C1(=CC=CC=C1)N[C@@H](CO)C(=O)O Chemical compound [Cu].C1(=CC=CC=C1)N[C@@H](CO)C(=O)O FLSHWSFJJIXMDU-QRPNPIFTSA-N 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZEIUNNMEXQHQMJ-UHFFFAOYSA-N benzaldehyde methylsulfonylmethane Chemical compound CS(=O)(=O)C.C(C1=CC=CC=C1)=O ZEIUNNMEXQHQMJ-UHFFFAOYSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 229960005091 chloramphenicol Drugs 0.000 description 1
- 229940097572 chloromycetin Drugs 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 208000021302 gastroesophageal reflux disease Diseases 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- -1 serine ethyl ester sulfuric acid Salt Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention is for the defect on existing DL- Su Shi-D-4-methylsulfonylphserine serine ethyl ester reaction post mother liquor processing technique, it provides in a kind of pmethylsulfonyl phenyleneserine copper synthesis D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester route, esterification filters to obtain D, the filtrate generated when L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester sulfate i.e. esterification mother liquor, D is obtained with suction filtration, the free D generated when L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor, mixing, distillation, hydrolysis, adjust pH, mantoquita preparation, recycle ethyl alcohol and mantoquita (i.e. pmethylsulfonyl phenyleneserine copper), the ethyl alcohol and pmethylsulfonyl phenyleneserine copper that the present invention recycles can be suitable for producing in next step.Substantially reduce COD in waste water, the cost for handling waste water substantially reduces, and product cost is declined.Sustainable development for reducing cost of material, reduction cost for wastewater treatment, enterprise is of great significance.
Description
Technical field
The invention belongs to medicine and chemical technology fields, are related to a series of broad-spectrum antiseptic of dedicated chloromycetins of new animal doctor
Preparation among medicine.It is recycled from D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor more specifically, being related to one kind
The method of mantoquita and ethyl alcohol.
Background technique
Chemical name：Pmethylsulfonyl phenyleneserine copper, English name 4-Methylsulfone Phenylserine Copper,
Structural formula is as follows.
The following are the more mature synthesis technologies of pmethylsulfonyl phenyleneserine copper：
Using, as reaction raw materials, water is reaction dissolvent to methyl sulfone benzaldehyde, glycine, copper sulphate, liquid alkaline synthesis pair is added dropwise
Methylsulfonyl benzene serine copper.
Florfenicol (Florfenicol) is a kind of new dedicated chloramphenicol of animal doctor successfully developed in the late nineteen eighties
The broad spectrum antibiotic of class.In recent years, demand is being continuously increased.
D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester is to prepare the important intermediate of Florfenicol.Currently, the intermediate
In preparation method hair, pmethylsulfonyl phenyleneserine copper route processing step is simple, is the D- Su Shi-that is widely used to methylsulfonyl benzene
Serine ethyl ester synthetic route.Therefore, pmethylsulfonyl phenyleneserine copper be the antimicrobial of the dedicated chloromycetin of animal doctor it is important in
The important synthesis material of mesosome D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester.
D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester pmethylsulfonyl phenyleneserine copper synthetic route is as follows：
Using pmethylsulfonyl phenyleneserine copper as reaction raw materials, suction filtration, gained filter cake are depressurized after ethyl alcohol, concentrated sulfuric acid reflux is added
For copper sulphate, gained filtrate decrease temperature crystalline, suction filtration, drying, filter cake D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester sulfuric acid
Salt, filtrate D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester esterification mother liquor；D, L- Su Shi-pmethylsulfonyl phenyleneserine
Vulcanized sodium precipitating copper ion is added in ethosulfate after being dissolved in water, active carbon is added and filters while hot, and pH, stirring are adjusted in filtrate cooling
After filter, gained filter cake is D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester, and gained filtrate is free D, L- ethyl ester mother liquor, D,
Through optical resolution after L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester, D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester is obtained.
Currently, esterification filters to obtain D in this route, when L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester sulfate, is produced
Raw filtrate, that is, D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester esterification mother liquor and suction filtration obtain D, and L- Su Shi-is to methyl sulfone
The free D generated when base benzene serine ethyl ester, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor are used as at industrial wastes
Reason, without good recoverying and utilizing method, greatly increase COD in industrial wastewater, while greatly improve wastewater treatment and product at
This.
Therefore, a kind of recycling ethyl alcohol and copper from the mother liquor that D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester are generated are studied
Salt (i.e. pmethylsulfonyl phenyleneserine copper) is particularly important.
Summary of the invention
The technical problem to be solved by the present invention is to for existing D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester to methylsulfonyl
Benzene serine copper synthetic route generates the defect on the processing technique of mother liquor, provides a kind of friendly environment and economic recycling work
Skill substantially reduces COD in waste water, and the cost for handling waste water substantially reduces, and product cost is declined.
To realize the above-mentioned technical purpose, the specific reaction equation of the present invention is as follows：
The technical scheme adopted by the invention is as follows：
One kind recycling pmethylsulfonyl phenyleneserine copper and ethyl alcohol from D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor
Method, the mother liquor is that pmethylsulfonyl phenyleneserine copper synthesizes D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester route and generates filter
Liquid the described method comprises the following steps：
S1：By esterification mother liquor and free D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor is according to 1:2-1:4
Mass ratio mixing, heating distillation, bottoms are spare, and the distillation gained further rectifying of fraction, recycling obtains ethyl alcohol；
In this step, since ethyl alcohol is mainly in esterification mother liquor, in esterification mother liquor and free D, L- Su Shi-right
Methylsulfonyl benzene serine ethyl ester mother liquor is less than 1:2 volume ratios mix, and sulfuric acid concentration is higher than 20% in mixed liquor, ethyl alcohol can be inhibited to steam
It distillates and, to reduce ethanol recovery, be higher than 1:4 volume ratio mixing, can make mixed liquor water become larger, make to distill
Ethyl alcohol water content is higher, to reduce the ethyl alcohol rectifying rate of recovery, therefore 1:2~1：Ethanol recovery is higher in 4 proportional regions, effect
Fruit is preferable.
S2：The bottoms that S1 distills keep the temperature 2-4 hours in 105 DEG C of -110 DEG C of hydrolysis decolorations, and reaction terminates, cooling
It to 30-60 DEG C, filters, gained filtrate is spare；
S3：Cupric sulfate pentahydrate is added in filtrate obtained by S2, lye adjusts pH=5-6.5, stirs 1 hour, filters drying, returns
Receipts obtain pmethylsulfonyl phenyleneserine copper；
Esterification mother liquor described in S1 is that esterification filters to obtain D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester sulfuric acid
The filtrate generated when salt, the free D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor are that synthesis end suction filtration obtains D,
The filtrate generated when L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester.
Further, esterification mother liquor described in S1 and free D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor matter
Amount is than being 1:2.
Further, vapo(u)rizing temperature described in S1 is 70-105 DEG C.
Further, which is characterized in that described in S2 hydrolyze the step of be：Directly utilize the sulfuric acid in former esterification mother liquor
It is hydrolyzed, does not need that new acid is added.
Further, decoloration described in S2 uses active carbon, the active carbon additional amount and esterification mother liquor and free D,
L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor mixed liquor is not less than 1：200, heat preservation to decoloration is completed.
Further, the mass ratio of cupric sulfate pentahydrate described in S3 and esterification mother liquor is 1:10~1:20.
The beneficial effects of the present invention are：
The present invention reacts the defect on post mother liquor processing technique for existing DL- Su Shi-D-4-methylsulfonylphserine serine ethyl ester,
A kind of friendly environment and economic new process are provided, pmethylsulfonyl phenyleneserine copper synthesizes D- Su Shi-pmethylsulfonyl phenyleneserine
In ethyl ester route, esterification filters to obtain esterification mother liquor and suction filtration obtains D, L- Su Shi-pmethylsulfonyl phenyleneserine second
Ethyl alcohol and mantoquita are recycled in the free D generated when ester, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor (i.e. to methylsulfonyl benzene
Serine copper), the ethyl alcohol and pmethylsulfonyl phenyleneserine copper that the present invention recycles can be suitable for producing in next step.Make in waste water
COD is substantially reduced, and the cost for handling waste water substantially reduces, and product cost is declined.For reducing cost of material, reducing waste water
The sustainable development of processing cost, enterprise is of great significance.
Specific embodiment
The present invention is made combined with specific embodiments below and further being elaborated, the embodiment is served only for explaining this
Invention, is not intended to limit the scope of the present invention.Test method as used in the following examples is normal unless otherwise specified
Rule method；Used material, reagent etc., unless otherwise specified, for the reagent and material commercially obtained.
Embodiment 1
Esterification mother liquor 300g is added into the three-necked flask of 1000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 600g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 105 DEG C of addition active carbon 5g, hydrolysis decoloration heat preservation 2 hours, is cooled to 30 DEG C, filters, cupric sulfate pentahydrate is added in filtrate
Liquid alkaline tune PH=5 is added dropwise in 16g, stirs 1 hour, filters drying.It the results are shown in Table 1
Embodiment 2
Esterification mother liquor 300g is added into the three-necked flask of 2000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 1200g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 110 DEG C of addition active carbon 7.5g, hydrolysis decoloration heat preservation 2 hours, is cooled to 30 DEG C, filters, five water sulfuric acid are added in filtrate
Liquid alkaline tune PH=5 is added dropwise in copper 16g, stirs 1 hour, filters drying.It the results are shown in Table 1
Embodiment 3
Esterification mother liquor 300g is added into the three-necked flask of 2000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 900g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 110 DEG C of addition active carbon 6g, hydrolysis decoloration heat preservation 2 hours, is cooled to 30 DEG C, filters, cupric sulfate pentahydrate is added in filtrate
Liquid alkaline tune PH=6.5 is added dropwise in 16g, stirs 1 hour, filters drying.It the results are shown in Table 1
Embodiment 4
Esterification mother liquor 300g is added into the three-necked flask of 2000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 1200g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 110 DEG C of addition active carbon 9g, hydrolysis decoloration heat preservation 2 hours, is cooled to 30 DEG C, filters, cupric sulfate pentahydrate is added in filtrate
Liquid alkaline tune PH=6.5 is added dropwise in 24g, stirs 1 hour, filters drying.It the results are shown in Table 1
Embodiment 5
Esterification mother liquor 300g is added into the three-necked flask of 1000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 600g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 105 DEG C of addition active carbon 5g, hydrolysis decoloration heat preservation 4 hours, is cooled to 30 DEG C, filters, cupric sulfate pentahydrate is added in filtrate
Liquid alkaline tune PH=6.5 is added dropwise in 10g, stirs 1 hour, filters drying.It the results are shown in Table 1
Embodiment 6
Esterification mother liquor 300g is added into the three-necked flask of 1000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 600g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 105 DEG C of addition active carbon 5.5g, hydrolysis decoloration heat preservation 4 hours, is cooled to 30 DEG C, filters, five water sulfuric acid are added in filtrate
Liquid alkaline tune PH=6 is added dropwise in copper 30g, stirs 1 hour, filters drying.It the results are shown in Table 1
Comparative example 1
Esterification mother liquor 300g is added into the three-necked flask of 1000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 300g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 105-110 DEG C of addition active carbon 5g, hydrolysis decoloration heat preservation 2 hours, is cooled to 30 DEG C, filters, five water sulphur are added in filtrate
Liquid alkaline tune PH=6 is added dropwise in sour copper 30g, stirs 1 hour, filters drying.It the results are shown in Table 1
Comparative example 2
Esterification mother liquor 600g is added into the three-necked flask of 1000ml, dissociate D, and L- Su Shi-is to methylsulfonyl benzene silk ammonia
Acetoacetic ester mother liquor 300g, after stirring, unlatching is heated to 70 DEG C of distillations, distills to 105 DEG C, rectifying column rectifying on ethyl alcohol；Mother liquor after
Continue in 105-110 DEG C of addition active carbon 5g, hydrolysis decoloration heat preservation 2 hours, is cooled to 30 DEG C, filters, five water sulphur are added in filtrate
Liquid alkaline tune PH=8 is added dropwise in sour copper 20g, stirs 1 hour, filters drying.It the results are shown in Table 1
The present invention reacts the defect on post mother liquor processing technique for existing DL- Su Shi-D-4-methylsulfonylphserine serine ethyl ester,
A kind of friendly environment and economic new process are provided, pmethylsulfonyl phenyleneserine copper synthesizes D- Su Shi-pmethylsulfonyl phenyleneserine
In ethyl ester route, esterification filters to obtain esterification mother liquor and suction filtration obtains D, L- Su Shi-pmethylsulfonyl phenyleneserine second
Ethyl alcohol and mantoquita are recycled in the free D generated when ester, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor (i.e. to methylsulfonyl benzene
Serine copper), the ethyl alcohol and pmethylsulfonyl phenyleneserine copper that the present invention recycles can be suitable for producing in next step.Make in waste water
COD is substantially reduced, and the cost for handling waste water substantially reduces, and product cost is declined.For reducing cost of material, reducing waste water
The sustainable development of processing cost, enterprise is of great significance.
Claims (6)
1. a kind of pmethylsulfonyl phenyleneserine copper and ethyl alcohol of being recycled from D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor
Method, the mother liquor are that pmethylsulfonyl phenyleneserine copper synthesizes D- Su Shi-D-4-methylsulfonylphserine serine ethyl ester route generation filtrate,
It is characterized in that, the described method comprises the following steps：
S1：By esterification mother liquor and free D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor is according to 1:2-1:4 quality
Ratio mixing, heating distillation, bottoms are spare, and the distillation gained further rectifying of fraction, recycling obtains ethyl alcohol；
S2：The bottoms that S1 distills keep the temperature 2-4 hours in 105 DEG C of -110 DEG C of hydrolysis decolorations, and reaction terminates, and is cooled to
It 30-60 DEG C, filters, gained filtrate is spare；
S3：Cupric sulfate pentahydrate is added in filtrate obtained by S2, lye adjusts pH=5-6.5, stirs 1 hour, filters drying, recycles
To pmethylsulfonyl phenyleneserine copper；
Esterification mother liquor described in S1 is that esterification filters to obtain D, when L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester sulfate
The filtrate of generation, the free D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor are that synthesis end suction filtration obtains D, L- Soviet Union
The filtrate generated when formula-D-4-methylsulfonylphserine serine ethyl ester.
2. the method according to claim 1, wherein esterification mother liquor and free D described in S1, L- Su Shi-right
Methylsulfonyl benzene serine ethyl ester mother liquor mass ratio is 1:2.
3. the method according to claim 1, wherein vapo(u)rizing temperature described in S1 is 70-105 DEG C.
4. the method according to claim 1, wherein the step of hydrolyzing described in S2 is：It is directly anti-using former esterification
It answers the sulfuric acid in mother liquor to be hydrolyzed, does not need that new acid is added.
5. the active carbon is added the method according to claim 1, wherein decoloration described in S2 uses active carbon
Amount is not less than 1 with esterification mother liquor and free D, L- Su Shi-D-4-methylsulfonylphserine serine ethyl ester mother liquor mixed liquor mass ratio：
200, heat preservation to decoloration is completed.
6. the method according to claim 1, wherein the quality of cupric sulfate pentahydrate described in S3 and esterification mother liquor
Than being 1:10~1:20.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705003A (en) * | 2019-01-25 | 2019-05-03 | 湖北中牧安达药业有限公司 | A kind of racemization method of L- D-4-methylsulfonylphserine serine ethyl ester |
| CN115073333A (en) * | 2022-07-20 | 2022-09-20 | 江苏八巨药业有限公司 | Racemization method based on active copper molecular sieve |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927054A (en) * | 1973-10-02 | 1975-12-16 | Sumitomo Chemical Co | Process for producing {62 -phenylserine copper complex |
| CN102617418A (en) * | 2012-02-21 | 2012-08-01 | 山东汉兴医药科技有限公司 | Method for recovering amino acid ester from amino acid esterification mother liquor |
| CN104130105A (en) * | 2014-06-25 | 2014-11-05 | 江苏九天高科技股份有限公司 | Method for recycling ethanol during production of p-methyl sulfonyl phenyl ethyl serinate |
| CN106748920A (en) * | 2016-11-11 | 2017-05-31 | 杭州新桂实业有限公司 | A kind of Florfenicol raw material DL ethyl ester preparation methods |
-
2018
- 2018-08-03 CN CN201810879167.8A patent/CN108912019A/en not_active Withdrawn
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3927054A (en) * | 1973-10-02 | 1975-12-16 | Sumitomo Chemical Co | Process for producing {62 -phenylserine copper complex |
| CN102617418A (en) * | 2012-02-21 | 2012-08-01 | 山东汉兴医药科技有限公司 | Method for recovering amino acid ester from amino acid esterification mother liquor |
| CN104130105A (en) * | 2014-06-25 | 2014-11-05 | 江苏九天高科技股份有限公司 | Method for recycling ethanol during production of p-methyl sulfonyl phenyl ethyl serinate |
| CN106748920A (en) * | 2016-11-11 | 2017-05-31 | 杭州新桂实业有限公司 | A kind of Florfenicol raw material DL ethyl ester preparation methods |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109705003A (en) * | 2019-01-25 | 2019-05-03 | 湖北中牧安达药业有限公司 | A kind of racemization method of L- D-4-methylsulfonylphserine serine ethyl ester |
| CN115073333A (en) * | 2022-07-20 | 2022-09-20 | 江苏八巨药业有限公司 | Racemization method based on active copper molecular sieve |
| CN115073333B (en) * | 2022-07-20 | 2024-01-19 | 江苏八巨药业有限公司 | Racemization method based on active copper molecular sieve |
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