CN102070572A - Method for recovering and preparing furanone acid from syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue - Google Patents
Method for recovering and preparing furanone acid from syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue Download PDFInfo
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Abstract
The invention discloses a method for recovering and preparing furanone acid from syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue. The technical points are that: 2-methoxyimino-2-(2-furyl)acetic acid is obtained by acidizing the syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue; pH is kept between 1.0 and 2.0; an oxidation reaction is performed on the 2-methoxyimino-2-(2-furyl)acetic acid and sodium nitrite under the action of a catalyst to obtain the solution of the furanone acid; and the solution of the furanone acid can be directly used as a raw material for synthesizing syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt. By the process, the 2-methoxyimino-2-(2-furyl)acetic acid in the syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue can be recovered to prepare the furanone acid, so that a waste material is turned into treasure; therefore, the method not only reduces pollution, but also has very good economic benefit.
Description
Technical field
The present invention relates to the Technology field of SMIA, relate to a kind of method for preparing the furans ketone acid that from the SMIA waste residue, reclaims in particular.
Background technology
SMIA (chemical name: (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate) be the important intermediate of s-generation cephalosporin analog antibiotic cephalofruxin, in preparation SMIA process furans ketone acid and methoxamine hydrochloride reaction process, (E)-2-methoxyimino-2-(furans-2-yl) acetate generation of 10～15% is arranged, and in treating process, there is a small amount of (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate to sneak in the waste residue, form " the SMIA waste residue " that be commonly called as in the industry, environmental protection treatment is formed very big pressure.
Summary of the invention
Goal of the invention of the present invention is to solve the waste residue that produces in the SMIA production process to handle, obtain 2-methoxyimino-2-(furans-2-yl) acetate through acidification, get the furanone acid solution with Sodium Nitrite generation oxidizing reaction, in the time of further can being used for preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate as raw material.
Technical scheme of the present invention is:
Develop a kind of method for preparing the furans ketone acid that reclaims from the SMIA waste residue, the main component in the SMIA waste residue is (E)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (I) and a small amount of (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (II):
It is characterized in that obtaining 2-methoxyimino-2-(furans-2-yl) acetate through acidification, pH remains on 1.0～2.0, gets the furanone acid solution with Sodium Nitrite generation oxidizing reaction under catalyst action, and its process is as follows:
Described SMIA waste residue: the mass ratio of Sodium Nitrite is 1: 1～3;
Described oxidizing reaction temperature is 40～90 ℃;
Described oxidation time is 3～8 hours;
The employed catalyzer of described oxidizing reaction is 85% phosphoric acid, potassiumphosphate, sodium phosphate or SODIUM PHOSPHATE, MONOBASIC;
The SMIA waste residue: the mass ratio of catalyzer is 1: 0.2～0.8.
The above-mentioned application of reclaiming preparation furans ketone acid from the SMIA waste residue is characterized in that when preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate as raw material.
The present invention has following advantage:
1. reactions steps is simple, and reaction is easy to control, and is with short production cycle;
2. the SMIA waste residue is utilized again, turn waste into wealth.
Embodiment:
Below in conjunction with embodiment the present invention is further set forth.
Embodiment 1
(mass ratio) waste residue: Ya Na: phosphoric acid=1: 2.504: 0.39
1. SMIA waste residue pre-treatment
Electronic stirring is being housed, add 56.7g SMIA waste residue in the 500ml flask of thermometer, add 200ml water and be heated to 25 ℃, add the 6g activated carbon, decoloured 1 hour, suction filtration, the hydrochloric acid with 30% (about 76ml) is used the 60ml dichloromethane extraction 4 times below the adjust pH to 0.5 at every turn, combining extraction liquid, decompression steams solvent, gets 2-methoxyimino-2-(furans-2-yl) acetate, and is standby.
Following examples herewith.
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, the phosphoric acid of 13ml 85% (proportion is amounted to 22.1g in 1.7), the hydrochloric acid of 35ml 30% is warmed up to 65～70 ℃, drips the hydrochloric acid of 111g sodium nitrite solution (being dissolved in 140ml water) and 50ml 30% simultaneously, drips about 5～6 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
The furanone acid solution cools to 20 ℃, adds the methoxamine hydrochloride of 50ml 41%, again with 30% sodium hydroxide adjusting pH=3.5～4.0,20～25 ℃ of insulation reaction 3.5 hours.In reaction solution, add 90g sodium-chlor, hydrochloric acid with 30% is adjusted to pH=0.5, again at every turn with 100ml dichloro extraction 4 times, combining extraction liquid cools to 0～5 ℃, feeds ammonia and transfers pH=8.0, suction filtration gets crude product 30.6g, refining (Z)-SMIA * elaboration 27.5g in methyl alcohol, in the SMIA waste residue, weight yield is 48.50%.
The elaboration detected result:
Outward appearance: faint yellow or yellow crystal powder;
Differentiate (HPLC): meet the requirements;
Content (HPLC): 〉=98.50%;
Moisture content (K.F.) :≤0.50%;
Transmittance :≤0.15%;
Trans-isomer(ide) :≤0.5%.
* (Z)-SMIA described herein promptly refers to chemical name (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate, (another name, methoxyimino furans ammonium acetate; (Z)-SMIA; English name is Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) product.Below each embodiment herewith illustrate.
Embodiment 2
(mass ratio) waste residue: Ya Na: sodium phosphate=1: 2.504: 0.55
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, 31.2g sodium phosphate, the hydrochloric acid of 85ml 30% is warmed up to 65～70 ℃, drip the hydrochloric acid of 111g sodium nitrite solution (being dissolved in 140ml water) and 50ml 30% simultaneously, drip about 3～4 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 21.4g, refining (Z)-SMIA elaboration 19.3g in methyl alcohol, in the SMIA waste residue, weight yield 34.04%.
Embodiment 3
(mass ratio) waste residue: Ya Na: potassiumphosphate=1: 2.504: 0.78
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, 44.3g potassiumphosphate, the hydrochloric acid of 85ml 30% is warmed up to 70～75 ℃, drip the hydrochloric acid of 111g sodium nitrite solution (being dissolved in 140ml water) and 50ml 30% simultaneously, drip about 5～6 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 19.9g, refining (Z)-SMIA elaboration 17.9g in methyl alcohol, in the SMIA waste residue, weight yield 31.57%.
Embodiment 4
(mass ratio) waste residue: Ya Na: SODIUM PHOSPHATE, MONOBASIC=1: 2.504: 0.4
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, 22.8g SODIUM PHOSPHATE, MONOBASIC, the hydrochloric acid of 55ml 30% is warmed up to 55～60 ℃, drip the hydrochloric acid of 111g sodium nitrite solution (being dissolved in 140ml water) and 50ml 30% simultaneously, drip about 4～5 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 17.8g, refining (Z)-SMIA elaboration 16.0g in methyl alcohol, in the SMIA waste residue, weight yield 28.22%.
Embodiment 5
(mass ratio) waste residue: Ya Na: phosphoric acid=1: 2.504: 0.48
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, the phosphoric acid of 16ml 85% (proportion is amounted to 27.2g in 1.7), the hydrochloric acid of 35ml 30% is warmed up to 40～45 ℃, the hydrochloric acid of while Dropwise 5 6.7g sodium nitrite solution (being dissolved in 60ml water) and 20ml 30%, drip about 6～7 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 12.7g, refining (Z)-SMIA elaboration 10.8g in methyl alcohol, in the SMIA waste residue, weight yield 19.05%.
Embodiment 6
(mass ratio) waste residue: Ya Na: phosphoric acid=1: 2.504: 0.17
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, 5.8ml 85% phosphoric acid (proportion is amounted to 9.86g in 1.7), the hydrochloric acid of 35ml 30% is warmed up to 85～90 ℃, drip the hydrochloric acid of 111g sodium nitrite solution (being dissolved in 140ml water) and 50ml 30% simultaneously, drip about 3～4 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 21.2g, refining (Z)-SMIA elaboration 18.5g in methyl alcohol, in the SMIA waste residue, weight yield 32.63%.
Embodiment 7
(mass ratio) waste residue: Ya Na: phosphoric acid=1: 2.504: 0.38
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, the phosphoric acid of 12.5ml85% (proportion is amounted to 21.25g in 1.7), the hydrochloric acid of 35ml 30% is warmed up to 40～45 ℃, drip the hydrochloric acid of 170g sodium nitrite solution (being dissolved in 140ml water) and 75ml 30% simultaneously, drip 7～8 hours (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 15.4g, refining (Z)-SMIA elaboration 13.8g in methyl alcohol, in the SMIA waste residue, weight yield 24.34%.
Embodiment 8
(mass ratio) waste residue: Ya Na: phosphoric acid=1: 2.504: 0.26
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, the phosphoric acid of 8.5ml85% (proportion is amounted to 14.45g in 1.7), the hydrochloric acid of 35ml 30% is warmed up to 50～55 ℃, drip the hydrochloric acid of 142g sodium nitrite solution (being dissolved in 180ml water) and 60ml 30% simultaneously, drip about 6～7 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 17.1g, refining (Z)-SMIA elaboration 15.4g in methyl alcohol, in the SMIA waste residue, weight yield 27.16%.
Embodiment 9
(mass ratio) waste residue: Ya Na: phosphoric acid=1: 1.499: 0.14
1. the pre-treatment of SMIA waste residue is with embodiment 1
2. above-mentioned 2-methoxyimino-2-(furans-2-yl) acetate, add 200ml water, the phosphoric acid of 4.5ml85% (proportion is amounted to 7.65g in 1.7), the hydrochloric acid of 35ml 30% is warmed up to 80～85 ℃, drip the hydrochloric acid of 85g sodium nitrite solution (being dissolved in 110ml water) and 45ml 30% simultaneously, drip about 4～5 hours of (reaction) time, pH remains on 1.0～2.0 in the dropping process, generates the furanone acid solution.
Furanone acid solution preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (methoxyimino furans ammonium acetate; (Z)-SMIA; Syn-2-Methoxyimino-2-(2-Furyl)-Acetic Acid-Ammonia Salt) process is with embodiment 1, the result is crude product 18.2g, refining (Z)-SMIA elaboration 16.3g in methyl alcohol, in the SMIA waste residue, weight yield 28.75%.
Claims (2)
1. one kind is reclaimed the method for preparing the furans ketone acid from the SMIA waste residue, and the main component in the SMIA waste residue is (E)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (I) and a small amount of (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate (II):
It is characterized in that obtaining 2-methoxyimino-2-(furans-2-yl) acetate through acidification, pH remains on 1.0～2.0, gets the furanone acid solution with Sodium Nitrite generation oxidizing reaction under catalyst action, and its process is as follows:
Described SMIA waste residue: the mass ratio of Sodium Nitrite is 1: 1～3;
Described oxidizing reaction temperature is 40～90 ℃;
Described oxidation time is 3～8 hours;
The employed catalyzer of described oxidizing reaction is 85% phosphoric acid, potassiumphosphate, sodium phosphate or SODIUM PHOSPHATE, MONOBASIC;
The SMIA waste residue: the mass ratio of catalyzer is 1: 0.2～0.8.
2. according to the described a kind of application of from the SMIA waste residue, reclaiming the method for preparing the furans ketone acid of claim 1, it is characterized in that when preparation (Z)-2-methoxyimino-2-(furans-2-yl) ammonium acetate as raw material.
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| CN201010592370A CN102070572B (en) | 2010-12-17 | 2010-12-17 | Method for recovering and preparing furanone acid from syn-2-methoxyimino-2-(2-furayl)-acetic acid-ammonia salt waste residue |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107011299A (en) * | 2017-03-24 | 2017-08-04 | 四平市精细化学品有限公司 | A kind of method that SMIA is reclaimed in the waste liquid from SMIA |
| CN107892678A (en) * | 2017-12-06 | 2018-04-10 | 成都化润药业有限公司 | The SMIA preparation technology of recyclable furans ketone acid |
| CN112010821A (en) * | 2020-09-29 | 2020-12-01 | 山东金城医药化工有限公司 | Recovery method of ethyl aminothiazoly loximate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932385A (en) * | 1971-05-14 | 1976-01-13 | Glaxo Laboratories Limited | Penicillins having a 6β-(α-etherified oximino) acylamido group |
| WO2004050663A2 (en) * | 2002-12-05 | 2004-06-17 | Orchid Chemicals & Pharmaceuticals Ltd | An improved process for the preparation of cefuroxime sodium |
| CN101538255A (en) * | 2009-04-02 | 2009-09-23 | 浙江拓普药业股份有限公司 | Preparing method of 2-methoxy imino group 2-furan ammonium acetate |
-
2010
- 2010-12-17 CN CN201010592370A patent/CN102070572B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3932385A (en) * | 1971-05-14 | 1976-01-13 | Glaxo Laboratories Limited | Penicillins having a 6β-(α-etherified oximino) acylamido group |
| WO2004050663A2 (en) * | 2002-12-05 | 2004-06-17 | Orchid Chemicals & Pharmaceuticals Ltd | An improved process for the preparation of cefuroxime sodium |
| CN101538255A (en) * | 2009-04-02 | 2009-09-23 | 浙江拓普药业股份有限公司 | Preparing method of 2-methoxy imino group 2-furan ammonium acetate |
Non-Patent Citations (1)
| Title |
|---|
| 《精细与专用化学品》 20040906 王荣耕等 头孢呋辛酸侧链--(Z)-2-甲氧亚氨基-2-(呋喃-2-基)乙酸铵 第10页左栏第1段～第11页右栏第6段 1-2 第12卷, 第17期 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103554069B (en) * | 2013-11-20 | 2015-07-22 | 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 |
| CN107011299A (en) * | 2017-03-24 | 2017-08-04 | 四平市精细化学品有限公司 | A kind of method that SMIA is reclaimed in the waste liquid from SMIA |
| CN107011299B (en) * | 2017-03-24 | 2019-05-31 | 四平市精细化学品有限公司 | A method of recycling furan ammonium salt from furan ammonium salt waste liquid |
| CN107892678A (en) * | 2017-12-06 | 2018-04-10 | 成都化润药业有限公司 | The SMIA preparation technology of recyclable furans ketone acid |
| CN112010821A (en) * | 2020-09-29 | 2020-12-01 | 山东金城医药化工有限公司 | Recovery method of ethyl aminothiazoly loximate |
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Address after: 255129 Zichuan District Economic Development Zone, Zibo, Shandong Co-patentee after: ZHONGSHAN JINCHENG DOBFAR PHARMACEUTICAL CO.,LTD. Patentee after: SHANDONG JINCHENG PHARMACEUTICAL GROUP CO.,LTD. Address before: 255129 Zichuan District Economic Development Zone, Zibo, Shandong Co-patentee before: ZHONGSHAN JINCHENG DOBFAR PHARMACEUTICAL CO.,LTD. Patentee before: SHANDONG JINCHENG PHARMACEUTICAL CO.,LTD. Address after: 255129 Zichuan District Economic Development Zone, Zibo, Shandong Co-patentee after: ZHONGSHAN JINCHENG DOBFAR PHARMACEUTICAL CO.,LTD. Patentee after: SHANDONG JINCHENG PHARMACEUTICAL CO.,LTD. Address before: 255129 Zichuan District Economic Development Zone, Zibo, Shandong Co-patentee before: ZHONGSHAN JINCHENG DOBFAR PHARMACEUTICAL CO.,LTD. Patentee before: SHANDONG JINCHENG PHARMACEUTICAL & CHEMICAL Co.,Ltd. |