CN106187960A - A kind of preparation method of 2 methoxyimino 2 furyl acetic acid ammonium salts - Google Patents
A kind of preparation method of 2 methoxyimino 2 furyl acetic acid ammonium salts Download PDFInfo
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Abstract
The invention provides the preparation method of a kind of 2 methoxyimino 2 furyl acetic acid ammonium salts, including: first by the compound of formula (I) structure and methoxamine reactant salt, obtain the reactant liquor containing formula (II) structural compounds, state addition basic hydrolysis in reactant liquor then up, obtain the reactant liquor containing formula (III) structural compounds, in the reactant liquor containing formula (III) structural compounds, add ammonia again become salt, obtain 2 methoxyimino 2 furyl acetic acid ammonium salts；The preparation method that the present invention provides is initiation material by selecting the compound of formula (I) structure, then react with methoxy propylhomoserin, and product is hydrolyzed, ammonium obtains target product, this reaction can complete the preparation from initiation material to end-product in same reaction system, need not the intermediate of separating reaction, and yield and the purity reacted are the highest.
Description
Technical field
The present invention relates to pharmaceutical synthesis field, particularly relate to the system of a kind of 2-methoxyimino-2-furyl acetic acid ammonium salt
Preparation Method.
Background technology
In second filial generation cephalosporins, cefuroxime is actual production and applies most antibiotic kinds,
It has huge consumption market and good development prospect.In requisite in cefuroxime preparation process
Mesosome, the preparation method of 2-methoxyimino-2-furyl acetyl ammonium salt has become as this area research worker focus of attention.
Shi Lanxiang etc. report at " cis-2-methoxy imino-2-furan acetic acid synthesising process research " with 2-furan first
Acid is initiation material, has synthesized 2-methoxy imino-2-furan acetic acid through thionyl chloride chlorination, cyanogen generation, hydrolysis, oximate.Improve
Cyanogen is for reaction method, the total recovery 45.9% of 2-methoxy imino-2-furan acetic acid.
Wang Ronggeng etc. report in " cefuroxime side chain-2-methoxyimino-2-(furyl) ammonium acetate " and use acetyl
Furan is initiation material, first carries out oximation reaction with nitrous acid and obtains 2-oximido-2-furan acetic acid；Then carry out instead with methoxamine
Should, obtain 2-methoxyimino-2-furan acetic acid；Finally being translated into ammonium salt, total recovery can reach 53%.
Jiang Junrong etc. report with furan as raw material, through acetyl in " synthesis of (S)-2-methoxy imino-2-furan acetic acid "
Change, oxime rearrangement, oximate synthesis 2-methoxy imino-2-furan acetic acid, total recovery 34%.
Jiang Yuren etc. are reported in phase transfer catalyst cetyl three in " synthesis of 2-methoxy imino-2-furan acetic acid "
Under the effect of methyl bromide ammonium, acetyl furan and benzaldehyde have synthesized 2-methoxy through aldol condensation, oxidation reaction and oximation reaction
Imido grpup-2-furan acetic acid.
Wang Yiding, Liu Xianghong " SMIA process study " middle age report SMIA synthesis technique in,
Furan acetic acid reacts with addition EDTA in methoxamine hydrochloride course of reaction, and salification process uses the side of methanol ammonia dropping
Method, yield reaches more than 60%.
It is initiation material that Chinese patent CN101538255 reports with acetyl furan, first carries out oximate, weight with nitrous acid
Row, hydrolysis obtain 2-oximido-2-furan acetic acid；Then react with methoxamine, obtain 2-methoxyimino-2-furan
Acetic acid；Finally being translated into ammonium salt, total recovery is 53%.
To sum up, the most employing acetyl furans carry out oximation reaction with nitrous acid, then carry out instead with methoxamine
Should, be translated into ammonium salt, after obtain 2-methoxyimino-2-furyl chloroacetic chloride through chlorinating agent chlorination method.This side
Method has the disadvantage in that 1, technique is loaded down with trivial details, to count for raw material from acetyl furan, will react through 4 steps, and overall yield of reaction is low；
2, environmental pollution is serious, releases substantial amounts of nitric oxide, nitrogen dioxide gas in acetyl furan with sodium nitrite course of reaction,
Operator's occupational health and environment had very big adverse effect.
Summary of the invention
In view of this, the technical problem to be solved is to provide a kind of 2-methoxyimino-2-furyl second
The preparation method of acid ammonium salt, the preparation method reaction condition that the present invention provides is gentle, and reaction yield is high.
The invention provides the preparation method of a kind of 2-methoxyimino-2-furyl acetic acid ammonium salt, including:
1) by the compound of formula (I) structure and methoxamine reactant salt, the reactant liquor containing formula (II) structural compounds is obtained,
Wherein, described R1Alkyl for C1～C8；
2) to step 1) reactant liquor containing formula (II) structural compounds that obtains adds basic hydrolysis, obtain containing formula
(III) reactant liquor of structural compounds,
3) in the reactant liquor containing formula (III) structural compounds, add ammonia and become salt, obtain 2-methoxyimino-2-furan
Guanidine-acetic acid ammonium salt.
Preferably, described step 1) in reaction catalyst be alkali carbonate, alkali metal carboxylate, alkali metal hydrogen-oxygen
One or more in compound, alkaline earth metal carbonate, alkaline earth metal carboxylation and alkaline earth metal carboxylation.
Preferably, described step 1) solvent that reacts is dichloromethane, dichloroethanes, chloroform, oxolane, second
One or more in ether, Nitrobenzol, Carbon bisulfide, chlorobenzene, carbon tetrachloride, methyl tertiary butyl ether(MTBE) and nitromethane.
Preferably, described step 1) temperature reacted is-20～60 DEG C.
Preferably, the compound of described formula (I) structure is 1:(1～3 with the mol ratio of described methoxy amine salt).
Preferably, the compound of described formula (I) structure prepares in accordance with the following methods: by furan and formula (IV) structure
Compound reacts, and obtains the compound of formula (I) structure,
Wherein, described R1For the alkyl of C1～C8,
Described X is Cl or Br.
Preferably, the catalyst that the compound of described furan and formula (IV) structure reacts be zinc dichloride, aluminum chloride, three
Boron fluoride, butter of tin, titanium chloride, iron chloride or Nickel dichloride..
Preferably, described step 2) in alkali be one or both in sodium hydroxide and potassium hydroxide.
Preferably, described step 2) in the consumption of alkali be to make step 2) pH value of the reactant liquor of hydrolysis is 10～11 i.e.
Can.
Preferably, described step 2) temperature reacted is 0～40 DEG C.
Compared with prior art, the invention provides the preparation side of a kind of 2-methoxyimino-2-furyl acetic acid ammonium salt
Method, including: first by the compound of formula (I) structure and methoxamine reactant salt, obtain the reaction containing formula (II) structural compounds
Liquid, states addition basic hydrolysis in reactant liquor then up, obtains the reactant liquor containing formula (III) structural compounds, then to containing formula
(III) reactant liquor of structural compounds adds ammonia and become salt, obtain 2-methoxyimino-2-furyl acetic acid ammonium salt；The present invention
The preparation method provided is initiation material by selecting the compound of formula (I) structure, then reacts with methoxy propylhomoserin, and will reaction
Product is hydrolyzed, ammonium obtains target product, and this reaction can complete from initiation material to end-product in same reaction system
Preparation, it is not necessary to the intermediate of separating reaction, and reaction yield and purity the highest；Test result indicate that, the present invention carries
The method total recovery of confession may be up to more than 67%, and trans by-product is less than 5%, and its purity is all more than 98%.
Accompanying drawing explanation
Fig. 1 prepares the reaction process of 2-methoxyimino-2-furyl acetic acid ammonium salt for the preparation method that the present invention provides
Figure.
Detailed description of the invention
The invention provides the preparation method of a kind of 2-methoxyimino-2-furyl acetic acid ammonium salt, including:
1) by the compound of formula (I) structure and methoxamine reactant salt, the reactant liquor containing formula (II) structural compounds is obtained,
Wherein, described R1Alkyl for C1～C8；
2) to step 1) reactant liquor containing formula (II) structural compounds that obtains adds basic hydrolysis, obtain containing formula
(III) reactant liquor of structural compounds,
3) in the reactant liquor containing formula (III) structural compounds, add ammonia and become salt, obtain 2-methoxyimino-2-furan
Guanidine-acetic acid ammonium salt.
According to the present invention, the present invention, by the compound of formula (I) structure and methoxamine reactant salt, obtains containing formula (II) structure
The reactant liquor of compound；Wherein, the compound of described formula (I) structure can be isolated single formula (I) compound or
Reactant liquor containing formula (I) structural compounds；Described R1Be preferably C2～C6 alkyl, more preferably methyl, ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl or n-octyl；Described reaction is additionally added
Catalyst, described catalyst is preferably alkali carbonate, alkali metal carboxylate, alkali metal hydroxide, alkaline-earth metal carbonic acid
One or more in salt, alkaline earth metal carboxylation and alkaline earth metal carboxylation, more preferably sodium carbonate, potassium carbonate, sodium acetate
With one or more in potassium acetate, the solvent of described reaction is preferably dichloromethane, dichloroethanes, chloroform, tetrahydrochysene furan
Mutter, one or more in ether, Nitrobenzol, Carbon bisulfide, chlorobenzene, carbon tetrachloride, methyl tertiary butyl ether(MTBE) and nitromethane, more
It is preferably dichloromethane or dichloroethanes；The mol ratio of the compound of described formula (I) structure and described methoxy amine salt be 1:(1～
3), more preferably 1:(1.1～2.5), more preferably 1:(1.5～2)；The compound of described formula (I) structure and described catalyst
Mol ratio be 1:(0.1～3), more preferably 1:(0.5～2.5), more preferably (1～2)；The temperature of described reaction is preferred
For-20～60 DEG C, more preferably-15～15 DEG C, most preferably-5～5 DEG C；The time of described reaction is preferably 2～12 hours,
More preferably 5～8 hours.
In the present invention, the compound of described formula (I) structure prepares the most in accordance with the following methods: by furan and formula (IV)
The compound reaction of structure, obtains the compound of formula (I) structure,
Wherein, described R1For the alkyl of the alkyl of C1～C8, more preferably C2～C6, more preferably methyl, ethyl, positive third
Base, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-hexyl, n-heptyl or n-octyl；Described X be preferably Cl or
Br；The catalyst of described reaction is zinc dichloride, aluminum chloride, boron trifluoride, butter of tin, titanium chloride, iron chloride or chlorination
Nickel, more preferably aluminum chloride or zinc dichloride；The solvent of described reaction be preferably dichloromethane, dichloroethanes, chloroform,
One in oxolane, ether, Nitrobenzol, Carbon bisulfide, chlorobenzene, carbon tetrachloride, methyl tertiary butyl ether(MTBE) and nitromethane or
Several, more preferably dichloromethane or dichloroethanes；Described furan is preferred with the mol ratio of the compound of described formula (IV) structure
For 1:(1～1.5), more preferably 1:(1.2～1.3)；Described furan is 1:(0.1～2.0 with the mol ratio of described catalyst),
More preferably 1:(0.5～1.0)；The group friend of described reaction is preferably-20～60 DEG C, more preferably-10～20 DEG C, most preferably
0～10 DEG C；The time of described reaction is preferably 2～12 hours, more preferably 8 hours；And in the present invention, the present invention by furan with
The reactant liquor of the compound containing formula (I) structure that the compound reaction of formula (IV) structure obtains can be directly used for and methoxy ammonium salt
Reaction, it is not necessary to separate.
According to the present invention, the present invention is to step 1) reactant liquor containing formula (II) structural compounds that obtains adds aqueous alkali
Solve, obtain the reactant liquor containing formula (III) structural compounds；Described alkali be preferably the one in sodium hydroxide and potassium hydroxide or
Two kinds；The concentration of described alkali is preferably 35%；The consumption of described alkali be preferably the anti-liquid liquid of hydrolysis pH most 10～
11, more preferably 10；The temperature of described reaction is preferably 0～40 DEG C, more preferably 10～30 DEG C；In the present invention, to containing
Before the reactant liquor of formula (II) structural compounds adds basic hydrolysis, also add in the reactant liquor containing formula (II) structural compounds
Water, wherein, the consumption of described water is the 5～30wt% of solvent quality；More preferably 10～20wt%；After completion of the reaction, this
Bright also include add acid for adjusting pH to 1, obtain the reactant liquor containing formula (III) structural compounds；Described acid is preferably hydrochloric acid.
According to the present invention, the present invention also adds ammonia in the reactant liquor containing formula (III) structural compounds and becomes salt, obtains 2-
Methoxyimino-2-furyl acetic acid ammonium salt；Ammonification is become the mode of salt not have particular/special requirement, those skilled in the art by the present invention
Suitable salifying method can be selected according to general knowledge known in this field.
The invention provides the preparation method of a kind of 2-methoxyimino-2-furyl acetic acid ammonium salt, including: first by formula
(I) compound of structure and methoxamine reactant salt, obtain the reactant liquor containing formula (II) structural compounds, state reaction then up
Liquid adds basic hydrolysis, obtains the reactant liquor containing formula (III) structural compounds, then to containing formula (III) structural compounds
Reactant liquor adds ammonia and becomes salt, obtain 2-methoxyimino-2-furyl acetic acid ammonium salt；Concrete reaction process is shown in that Fig. 1, Fig. 1 are
The preparation method that the present invention provides prepares the reacting flow chart of 2-methoxyimino-2-furyl acetic acid ammonium salt；The present invention provides
Preparation method be initiation material by selecting the compound of formula (I) structure, then react with methoxy propylhomoserin, and by product
Be hydrolyzed, ammonium obtains target product, and this reaction can complete the system from initiation material to end-product in same reaction system
Standby, it is not necessary to the intermediate of separating reaction, simplify production technology, reduce production cost, and the yield of reaction and purity are all
The highest；Additionally, the present invention is initiation material by selecting formula (I) compound, also significantly improve isomer selective, trans pair
The content of product reduces.
Technical scheme below in conjunction with the embodiment of the present invention is clearly and completely described, it is clear that described enforcement
Example is only a part of embodiment of the present invention rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under not making creative work premise, broadly falls into the model of present invention protection
Enclose.
Embodiment 1
1) in reaction vessel, 136g (2.00mol) furan, 500g dichloromethane and 136g (1.0mol) dichloride are added
Zinc.Control reaction temperature, at 10 DEG C, drips 382g (2.8mol) chloro ethanedioic acid methyl ester.Drip complete, continue reaction 6h.Reaction
Terminate, reactant mixture is added to the water.Stirring, extract and separate, obtain the organic facies containing 2-oxo furyl acetas straight
Connect as the next step.
2) to step 1) organic facies containing 2-oxo furyl acetas that obtains adds 414g (3.0mol) carbonic acid
Potassium.System temperature is maintained at 0 DEG C, is slowly added to 184g (2.2mol) methoxamine hydrochloride, and the joining day is no less than 1 hour.Add
Finish, continue to react 8h at 0 DEG C.HPLC monitors trans by-product less than 5%.Reaction terminates, and obtains containing product cis-2-methoxy sub-
The solution system of amino-2-furyl methyl acetate can be directly used as next step.
Product cis-2-methoxyimino-2-furyl the methyl acetate obtaining this step carries out magnetic resonance detection:1H
NMR(300MHz CDCl3)δ7.53(d,1H),7.31(d,1H),6.54(dd,1H),4.15(s,3H),3.94(s,3H)。
3) to step 2) solution that obtains adds 50g water, adding strong lye regulation pH value is 10.Reaction 6h.Add salt
Acid regulation pH value is 1.Separatory.Ammonia, a large amount of Precipitations it are passed through in organic facies.Filter, dry, it is thus achieved that 2-methoxy imido
Base-2-furyl acetic acid ammonium salt 252g, 3 step total recoverys 67.7%；Purity is 98.4%
2-methoxyimino-2-furyl acetic acid the ammonium salt obtained is carried out nuclear-magnetism detection:1H NMR(300MHz,CD3OD)
δ7.59(s,1H),6.57(s,1H),6.52(s,1H),4.95(s,4H),3.89(s,3H)。
Embodiment 2
1) in reaction vessel, 136g (2.00mol) furan, 500g dichloroethanes and 80g (0.6mol) tri-chlorination are added
Aluminum, control reaction temperature, at 10 DEG C, drips 300g (2.2mol) chloro ethanedioic acid ethyl ester.Drip complete, continue reaction 6h.Reaction
Terminate, reactant mixture is added to the water.Stirring, extract and separate.Obtain the organic facies containing 2-oxo furyl acetas straight
Connect as the next step.
2) to step 1) organic facies containing 2-oxo furyl acetas that obtains adds 328g (4.0mol) acetic acid
Sodium.System temperature is maintained at 0 DEG C, is slowly added to 250g (3.0mol) methoxamine hydrochloride, and the joining day is no less than 1 hour.Add
Finish, continue to react 8h at 0 DEG C.HPLC monitors trans by-product less than 5%.Reaction terminates, and reaction terminates, and obtains containing product suitable
The solution system of formula-2-methoxyimino-2-furyl methyl acetate can be directly used as next step.
Product cis-2-methoxyimino-2-furyl the methyl acetate obtaining this step carries out magnetic resonance detection:1H
NMR(300MHz CDCl3) δ 7.53 (d, 1H), 7.31 (dd, 1H), 6.53 (dd, 1H), 4.41 (q, 2H), 4.14 (s, 3H),
1.40(t,3H)。
3) to step 2) solution that obtains adds 50g water, adding strong lye regulation pH value is 10.Reaction 6h.Add salt
Acid regulation pH value is 1.Separatory.Ammonia, a large amount of Precipitations it are passed through in organic facies.Filter, dry, it is thus achieved that product 261g, always
Yield 70.2%, purity is 98.1%.
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention.It is right to it should be pointed out that,
For those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention is carried out
Some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Claims (10)
1. a preparation method for 2-methoxyimino-2-furyl acetic acid ammonium salt, including:
1) by the compound of formula (I) structure and methoxamine reactant salt, the reactant liquor containing formula (II) structural compounds is obtained,
Wherein, described R1Alkyl for C1～C8；
2) to step 1) reactant liquor containing formula (II) structural compounds that obtains adds basic hydrolysis, obtain containing formula (III)
The reactant liquor of structural compounds,
3) in the reactant liquor containing formula (III) structural compounds, add ammonia and become salt, obtain 2-methoxyimino-2-furyl second
Acid ammonium salt.
Preparation method the most according to claim 1, it is characterised in that described step 1) in reaction catalyst be alkali metal
Carbonate, alkali metal carboxylate, alkali metal hydroxide, alkaline earth metal carbonate, alkaline earth metal carboxylation and alkaline-earth metal carboxylic
One or more in hydrochlorate.
Preparation method the most according to claim 1, it is characterised in that described step 1) solvent that reacts be dichloromethane,
Dichloroethanes, chloroform, oxolane, ether, Nitrobenzol, Carbon bisulfide, chlorobenzene, carbon tetrachloride, methyl tertiary butyl ether(MTBE) and
One or more in nitromethane.
Preparation method the most according to claim 1, it is characterised in that described step 1) temperature reacted is-20～60 DEG C.
Preparation method the most according to claim 1, it is characterised in that the compound of described formula (I) structure and described methoxy
The mol ratio of amine salt is 1:(1～3).
Preparation method the most according to claim 1, it is characterised in that the compound of described formula (I) structure is according to lower section
Method prepares: reacted by the compound of furan with formula (IV) structure, obtains the compound of formula (I) structure,
Wherein, described R1For the alkyl of C1～C8,
Described X is Cl or Br.
Preparation method the most according to claim 6, it is characterised in that described furan reacts with the compound of formula (IV) structure
Catalyst be zinc dichloride, aluminum chloride, boron trifluoride, butter of tin, titanium chloride, iron chloride or Nickel dichloride..
Preparation method the most according to claim 1, it is characterised in that described step 2) in alkali be sodium hydroxide and hydrogen-oxygen
Change in potassium one or both.
Preparation method the most according to claim 1, it is characterised in that described step 2) in the consumption of alkali for making step 2) water
The pH value of the reactant liquor solving reaction is 10～11.
Preparation method the most according to claim 1, it is characterised in that described step 2) temperature reacted is 0～40 DEG C.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194644A (en) * | 2020-09-01 | 2021-01-08 | 河南立诺制药有限公司 | Alkali metal salt of furan, furoyl chloride and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357911A (en) * | 2008-09-19 | 2009-02-04 | 江苏爱利思达清泉化学有限公司 | Method for synthesizing (z)-2-(alpha-methoxyimino)furan-ammonium acetate |
| 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 |
-
2016
- 2016-07-14 CN CN201610555850.7A patent/CN106187960B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101357911A (en) * | 2008-09-19 | 2009-02-04 | 江苏爱利思达清泉化学有限公司 | Method for synthesizing (z)-2-(alpha-methoxyimino)furan-ammonium acetate |
| 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 |
Non-Patent Citations (3)
| Title |
|---|
| 史兰香等: "顺式-2-甲氧亚胺基-2-呋喃乙酸合成工艺研究", 《河北科技大学学报》 * |
| 向纪明等: "芳基乙酮酸乙酯的合成新方法", 《有机化学》 * |
| 武金鸿: "（Z）-甲氧亚胺基呋喃乙酸铵盐制备工艺的研究", 《硕士学位论文》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112194644A (en) * | 2020-09-01 | 2021-01-08 | 河南立诺制药有限公司 | Alkali metal salt of furan, furoyl chloride and preparation method thereof |
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