CN1051170A - The synthetic method of oxoamino-aliphatic carboxylic acid - Google Patents
The synthetic method of oxoamino-aliphatic carboxylic acid Download PDFInfo
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- CN1051170A CN1051170A CN 89108213 CN89108213A CN1051170A CN 1051170 A CN1051170 A CN 1051170A CN 89108213 CN89108213 CN 89108213 CN 89108213 A CN89108213 A CN 89108213A CN 1051170 A CN1051170 A CN 1051170A
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- phthalimide
- oxoamino
- aliphatic carboxylic
- carboxylic acid
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Abstract
The novel synthesis of oxoamino-aliphatic carboxylic acid, with Tetra hydro Phthalic anhydride (I) is starting raw material, obtain N-hydroxyl phthalimide (II) with oxammonium hydrochloride and alkaline carbonate reaction, again (II) and bromo carboxylicesters and tertiary amine are done under the situation of solvent at polar solvent DMF etc., reaction makes phthalimide an oxygen-1-carboxylate (III), then with (III) and hydrochloric acid reflux together, behind the elimination phthalic acid, obtain oxoamino-aliphatic carboxylic acid hydrochloride (IV) with ethanol and ethyl acetate backflow again.
Description
Synthesizing of oxoamino-aliphatic carboxylic acid, its structural formula is:
R wherein
1, R
2Be C
1-C
4Alkyl, n=0～4.
The technical field of the invention is the synthetic of oxoamino-aliphatic carboxylic acid.
Oxoamino-aliphatic carboxylic acid is a semisynthetic penicillin, the important intermediate that cynnematin and monocycle beta-lactam microbiotic are complete synthesis, thereby this compound is synthetic significant, through consulting U.S. chemical abstract, Soviet Union's chemical abstracts, moral temperature thing patent documentation does not find the synthetic method of the described oxoamino-aliphatic carboxylic acid of relevant this patent as yet.
The objective of the invention is 692-3,1962 according to (1) Von.H.Gross etal:Journal furprak tische chemic; (2) Annie rougoxy etal:Bulletin DE Lasoiete chimique DE France 5-6 833-38,1976; (3) D.Mc Hale etal:J.CHem.soc, the chemosynthesis principle in 255 1960, the novel synthesis of oxoamino-aliphatic carboxylic acid has been invented in design.This method is simple to operate, and the yield height is easy to suitability for industrialized production, and three-waste pollution is easy to control, and by product can utilize.
Concrete synthesis step of the present invention is to make starting raw material with Tetra hydro Phthalic anhydride (I), reacts 15～30 minutes at 80 ℃～100 ℃ with oxammonium hydrochloride and alkali-metal carbonate, has reacted the postcooling filtration and has obtained N-hydroxyl phthalimide (II).Again with N-hydroxyl phthalimide (II) and bromo carboxylicesters and tertiary amine
Using dimethyl formamide (DMF), dimethyl sulfoxide (DMSO) or dioxane polar solvent are done under the situation of reaction solvent, and control reaction temperature is 30 ℃～90 ℃, reacts 6～16 hours.Make the used tertiary amine of phthalimide-oxygen-fat carboxylic ether (III)
Middle R
1, R
2, R
3Can be the alkane of C1～C4, reaction solvent can be a polar solvent, as dimethyl formamide, and dimethyl sulfoxide (DMSO), dioxane, the structure of bromo carboxylicesters is:
Wherein R1, R2, R3 are the alkyl of C1～C4, n=0～4.Then earlier with phthalimide-oxygen-fat carboxylic ether (III) with (2-12N's) hydrochloric acid reflux, filtered in 4-12 hour behind the phthalic acid again and ethanol and ethyl acetate backflow, obtain the hydrochloride (IV) of oxoamino-aliphatic carboxylic acid.Reactional equation is as follows:
The invention has the advantages that this synthetic method is easy and simple to handle, be easy to realize suitability for industrialized production, reaction yield height, three-waste pollution are easy to control, and by product can be used.
Embodiment:
With the 10g(0.14 mol) oxammonium hydrochloride, the 7.62g(0.07 mol) yellow soda ash input reaction flask, add 38.5ml water and stir, be heated to 30～80 ℃.Under stirring fast, in 10～30 minutes, the 16.9g(0.14 mol) Tetra hydro Phthalic anhydride input reaction flask.80～100 ℃ the reaction 15～30 minutes, cool off, filter, wash pistac N-hydroxyl phthalimide, yield 80～85%, mp227-229 ℃.
With the 11.5g(0.07 mol) the N-phthalimide, 27.5mlDMF drops into reaction flask, is heated to 30～50 ℃, makes it clear and bright.Add the 18g(0.085 mol then) isobutyl ethyl bromide, generate the light green clear liquor.Add the 11.9g(0.1 mol again) triethylamine, react on 30～90 ℃ of stirring reactions 6～16 hours, be cooled to room temperature and filter.Filtrate (red-brown) is injected the 188g trash ice slowly, is stirred to ice and all melts, and leaches the pale precipitation thing, washing, dry 2-phthalimide oxygen-2,2-dimethyl acetic acid ethyl ester, the yield 70～85% of getting.Mp76～77 ℃, ultimate analysis theoretical value: C59.77; H5.206; N5.39.Measured value: C60.31; H5.43; N5.28.
With the 13g(0.046 mol) 2-phthalimide-oxygen-2.2-dimethyl acetic acid ethyl ester, 40ml2-12N hydrochloric acid drops into reaction flask, is heated to 60～80 ℃ of reactions 4～12 hours, is chilled to room temperature, separates out crystallization, and low temperature was placed liquid.Leach phthalic acid next day, faint yellow filtrate evaporated under reduced pressure is extremely done, get the yellow solid small-particle, add 2ml ethanol and 15ml ethyl acetate, reflux 30 minutes, after being cooled to room temperature, at 5 ℃ of placements filtration washing next day that spends the night, white small-particle crystallization, drying makes 7.0g2-aminooxy-2.2-diformazan acetic acid hydrochloride, content is more than 98%, yield 80～90%.m·p·164-166℃。Ultimate analysis theoretical value: c30.85; C16.42; N9.00.Measured value: C31.67; H6.40; N8.96.Mass spectrum: 119m/l; 74m/l; 59m/l; 44m/l.
Claims (3)
1, a kind of method of synthetic oxoamino-aliphatic carboxylic acid, it is characterized in that using Tetra hydro Phthalic anhydride (I), oxammonium hydrochloride and alkali-metal carbonate reaction obtain N-hydroxyl phthalimide (II), again N-hydroxyl phthalimide (II) and bromoalkane acid esters and tertiary amine are being used dimethylformamide (DMF), dimethyl sulfoxide (DMSO), the dioxane polar solvent is done under the situation of reaction solvent, reaction makes phthalimide one oxygen, one fat carboxylic ether (III), then with phthalimide one oxygen, one fatty carboxylic esters (III) and hydrochloric acid reflux together, after filtering phthalic acid, concentrated filtrate is to doing, and last and ethanol and ethyl acetate backflow obtain the hydrochloride (IV) of oxoamino-aliphatic carboxylic acid.
2, according to the method for the described synthetic oxoamino-aliphatic carboxylic acid of claim 1, it is characterized in that Tetra hydro Phthalic anhydride and oxammonium hydrochloride and alkali-metal carbonate reaction, temperature of reaction is controlled at 80 ℃～100 ℃, reaction times is 15～30 minutes, has reacted the postcooling filtration and has obtained N-hydroxyl phthalimide (II).
3, according to claim 1, the method for synthetic oxoamino-aliphatic carboxylic acid is characterized in that N-hydroxyl phthalimide (II) and bromoalkane carboxylicesters and tertiary amine
React in reaction solvent, make phthalimide one oxygen, one fatty acid ester (III), temperature of reaction is 30 ℃～90 ℃, 6～16 hours reaction times.Tertiary amine
In R
1, R
2, R
3Can be C
2-C
4Alkane, reaction solvent can be a polar solvent, as dimethyl formamide, dimethyl sulfoxide (DMSO), dioxane.The structure of bromoalkane carboxylicesters is
Wherein R1, R
2, R
3Be C
1～C
4Alkyl n=0～4
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108213 CN1051170A (en) | 1989-10-25 | 1989-10-25 | The synthetic method of oxoamino-aliphatic carboxylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108213 CN1051170A (en) | 1989-10-25 | 1989-10-25 | The synthetic method of oxoamino-aliphatic carboxylic acid |
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| CN1051170A true CN1051170A (en) | 1991-05-08 |
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| CN 89108213 Pending CN1051170A (en) | 1989-10-25 | 1989-10-25 | The synthetic method of oxoamino-aliphatic carboxylic acid |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073989C (en) * | 1999-06-15 | 2001-10-31 | 中国科学院广州化学研究所 | Synthesis process of N-hydroxyl phthalimide |
| US6316639B1 (en) | 1999-09-07 | 2001-11-13 | Consortium für elektrochemische Industrie GmbH | Process for the preparation of cyclic N-hydroxydicarboximides |
| CN1953963B (en) * | 2004-05-17 | 2010-05-26 | 大赛璐化学工业株式会社 | Process for producing cyclic N-hydroxyimide compound |
| CN101845012A (en) * | 2010-02-10 | 2010-09-29 | 李瑞菊 | Method for synthesizing N-hydroxy phthalimide with solid-phase process |
| CN102911085A (en) * | 2012-10-24 | 2013-02-06 | 甘肃省化工研究院 | Synthesis process of compound D-2- aminoxy-3-methylbutyric acid |
| US8658804B2 (en) | 2009-04-01 | 2014-02-25 | Exxonmobil Chemical Patents Inc. | Process for preparing N-substituted cyclic imides |
| CN106831535A (en) * | 2016-12-19 | 2017-06-13 | 南京红宝丽醇胺化学有限公司 | A kind of method that low corrosion produces N hydroxyphthalimides |
| WO2017204936A1 (en) | 2016-05-26 | 2017-11-30 | Exxonmobil Chemical Patents Inc. | Production of cyclic imides suitable for oxidation catalysis |
| WO2017204935A1 (en) | 2016-05-26 | 2017-11-30 | Exxonmobil Chemical Patents Inc. | Production of cyclic imides suitable for oxidation catalysis |
| WO2018075176A1 (en) | 2016-10-18 | 2018-04-26 | Exxonmobil Chemical Patents Inc. | Cyclic imide slurry compositions |
-
1989
- 1989-10-25 CN CN 89108213 patent/CN1051170A/en active Pending
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1073989C (en) * | 1999-06-15 | 2001-10-31 | 中国科学院广州化学研究所 | Synthesis process of N-hydroxyl phthalimide |
| US6316639B1 (en) | 1999-09-07 | 2001-11-13 | Consortium für elektrochemische Industrie GmbH | Process for the preparation of cyclic N-hydroxydicarboximides |
| CN1953963B (en) * | 2004-05-17 | 2010-05-26 | 大赛璐化学工业株式会社 | Process for producing cyclic N-hydroxyimide compound |
| US8658804B2 (en) | 2009-04-01 | 2014-02-25 | Exxonmobil Chemical Patents Inc. | Process for preparing N-substituted cyclic imides |
| CN101845012A (en) * | 2010-02-10 | 2010-09-29 | 李瑞菊 | Method for synthesizing N-hydroxy phthalimide with solid-phase process |
| CN102911085A (en) * | 2012-10-24 | 2013-02-06 | 甘肃省化工研究院 | Synthesis process of compound D-2- aminoxy-3-methylbutyric acid |
| US11014883B2 (en) | 2016-05-26 | 2021-05-25 | Exxonmobil Chemical Patents Inc. | Production of cyclic imides suitable for oxidation catalysis |
| US11161812B2 (en) | 2016-05-26 | 2021-11-02 | Exxonmobil Chemical Patents Inc. | Production of cyclic imides suitable for oxidation catalysis |
| WO2017204936A1 (en) | 2016-05-26 | 2017-11-30 | Exxonmobil Chemical Patents Inc. | Production of cyclic imides suitable for oxidation catalysis |
| WO2017204935A1 (en) | 2016-05-26 | 2017-11-30 | Exxonmobil Chemical Patents Inc. | Production of cyclic imides suitable for oxidation catalysis |
| WO2018075176A1 (en) | 2016-10-18 | 2018-04-26 | Exxonmobil Chemical Patents Inc. | Cyclic imide slurry compositions |
| US10584096B2 (en) | 2016-10-18 | 2020-03-10 | Exxonmobil Chemical Patents Inc. | Cyclic imide slurry compositions |
| CN106831535A (en) * | 2016-12-19 | 2017-06-13 | 南京红宝丽醇胺化学有限公司 | A kind of method that low corrosion produces N hydroxyphthalimides |
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