CN101845012B - Method for synthesizing N-hydroxy phthalimide with solid-phase process - Google Patents
Method for synthesizing N-hydroxy phthalimide with solid-phase process Download PDFInfo
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- CN101845012B CN101845012B CN2010101086656A CN201010108665A CN101845012B CN 101845012 B CN101845012 B CN 101845012B CN 2010101086656 A CN2010101086656 A CN 2010101086656A CN 201010108665 A CN201010108665 A CN 201010108665A CN 101845012 B CN101845012 B CN 101845012B
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- Prior art keywords
- solid
- synthesizing
- phase process
- phthalic anhydride
- hydroxyphthalimide
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- 238000000034 method Methods 0.000 title claims abstract description 25
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 230000008569 process Effects 0.000 title claims abstract description 11
- 230000002194 synthesizing effect Effects 0.000 title abstract description 4
- 239000007790 solid phase Substances 0.000 title abstract 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims abstract description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 5
- 238000005516 engineering process Methods 0.000 claims description 5
- YOBAEOGBNPPUQV-UHFFFAOYSA-N iron;trihydrate Chemical compound O.O.O.[Fe].[Fe] YOBAEOGBNPPUQV-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 abstract 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 abstract 1
- 239000011780 sodium chloride Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000003746 solid phase reaction Methods 0.000 description 3
- 238000010671 solid-state reaction Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KMOUUZVZFBCRAM-OLQVQODUSA-N (3as,7ar)-3a,4,7,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C=CC[C@@H]2C(=O)OC(=O)[C@@H]21 KMOUUZVZFBCRAM-OLQVQODUSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010200 validation analysis Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Indole Compounds (AREA)
Abstract
The invention discloses a method for synthesizing N-hydroxy phthalimide with the solid-phase process by grinding the raw materials of phthalic anhydride and hydroxylamine hydrochloride and the mineralizer of sodium chloride and ferric oxide under the protection of nitrogen. The method for synthesizing N-hydroxy phthalimide with the solid-phase process ensures the thorough reaction, high yield, low energy consumption and less pollution and is suitable for industrial production, thereby being a promising preparation method.
Description
Invention field
The present invention relates to a kind of method of solid phase method synthetic compound, be specifically related to compound N-hydroxyphthalimide solid phase synthesis process of (being called for short HP), belong to chemosynthesis technical field.
Background technology
HP is a kind of important chemical material, can because it contains N-OH, generate radical easily as the midbody of synthetic drugs and sterilant, therefore also can be used as the middle amboceptor that transmits electronics in the electrochemical oxidation reactions.In recent years, HP is applied to the electron transit mediator of electrochemical reaction, and the amboceptor material in the pulp bio-bleaching technology, and the potential application prospect will be arranged, so the Study of synthesis method of this compound seems and becomes more and more important.
About synthesizing of HP, it has disclosed its compound method as intermediate product among the one Chinese patent application prospectus CN1051170A (1991); Adopt Tetra hydro Phthalic anhydride and oxammonium hydrochloride as raw material; As reaction solvent, add alkaline matters such as yellow soda ash with water, promote that molecular balance transforms to the product direction; Obtain the N-hydroxyphthalimide after the reaction, productive rate reaches 80～85%.Chinese patent CN1073989C has done the improvement of reaction system to the compound body of HP.
Above-mentioned compound method has all adopted conventional liquid-phase reaction system, has the deficiency that contaminated wastewater, energy consumption are high, yield is low.
Solid state reaction is that solid is participated in the direct chemical reaction, and chemical transformation takes place, simultaneously at least at a solid interior or an outside chemical reaction that the process control is used.Solid state reaction is in the material of any state of aggregation; Because the influence of thermal motion; Even be in molecule, atom or particle on the lattice point, more or less all might moment depart from normal equilibrium theory of tide, these particles (even hole) can produce diffusion under the concentration difference factor drives.The contact of solid-state reactants particle and diffusion are that the solid product nucleus is able to form and the continuous essential condition of growth.Solid state reaction is not used solvent, has highly selective, high yield, simple technological process and other advantages, has become the important method that people prepare chemical.
Summary of the invention
The object of the present invention is to provide the method for the synthetic N-hydroxyphthalimide of a kind of solid phase method, this method has the selectivity height, yield is high, technological process is simple, energy consumption is low, is fit to industrial production, has good application prospects.
The objective of the invention is to realize like this: the method for the synthetic N-hydroxyphthalimide of a kind of solid phase method, its preparation technology is following:
(1), mixes phthalic anhydride and sodium-chlor by 1: 0.001 weight ratio fully grinding;
(2), 1.008 times the oxammonium hydrochloride that in said mixture, adds the phthalic anhydride amount;
(3), 0.001 times the red oxide of iron that in said mixture, adds oxammonium hydrochloride weight;
(4), said mixture, under 90 ± 5 ℃, fully ground 4～5 hours, reduce to room temperature, the washing, the oven dry, the N-hydroxyphthalimide.
In reaction process, take sodium-chlor and red oxide of iron as mineralizer, quicken the formation speed of nucleus, improve crystalline network.In process of lapping, need to use nitrogen protection, can promote the carrying out of chemical reaction like this, improve product gas purity.
The product that adopts method preparation of the present invention produces a desired effect all through infrared, absorption spectrum, ultimate analysis, performance liquid chromatography detection validation.This law has adopted brand-new reaction system, has not only improved yield of product and purity, and after reaction is accomplished, is easy to separate, and makes the synthetic process become efficient, safe green reaction process.
The present invention adopts solid phase synthesis process to prepare the N-hydroxyphthalimide, and selectivity is high, yield is high, technological process is simple, energy consumption is low, and resulting product only need can satisfy industrial application according to method removal moisture and other impurity of routine.
Table one: product ultimate analysis
| Blank amount/% | Actual measured amount/% | Theoretical amount/% | |
| N | 0.016 | 8.637 | 8.582 |
| C | 0.006 | 58.g0 | 58.85 |
| H | 0.008 | 3.158 | 3.065 |
Table two: the comparison of the present invention and prior art
| Prior art | The present invention | |
| Outward appearance | Little yellow crystalline powder | White is to off-white powder |
| Fusing point/℃ | 233-235 | 232-234 |
| Massfraction/% | 95-97 | 98.5 more than |
| Yield/% | 80-93 | 95.5-99.0 |
Specific embodiment
Below, foregoing of the present invention is done further to specify, but should this be interpreted as that the scope of above-mentioned theme of the present invention only limits to following embodiment through the embodiment of embodiment form.All technology that realizes based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
Get phthalic anhydride 37.4g, sodium-chlor 37.4mg mixes, and under nitrogen protection, grinds 4.5 hours.Add oxammonium hydrochloride 17.7g again, red oxide of iron 17.7mg, under the nitrogen protection, 90 ℃ were ground 4 hours, washing, oven dry gets white solid 38.3g, purity 98.5%.
Embodiment 2
Get phthalic anhydride 74.0g, sodium-chlor 74mg mixes, and under nitrogen protection, grinds 4.5 hours.Add oxammonium hydrochloride 35g again, red oxide of iron 35mg, under the nitrogen protection, 95 ℃ were ground 5 hours, washing, oven dry gets white solid 77.0g, purity 98.0%.
Claims (1)
1. the method for the synthetic N-hydroxyphthalimide of a solid phase method, it is characterized in that its technology is following: following process of lapping needs nitrogen protection,
(1), mixes phthalic anhydride and sodium-chlor by 1: 0.001 weight ratio fully grinding;
(2), 1.008 times the oxammonium hydrochloride that in said mixture, adds the phthalic anhydride amount;
(3), 0.001 times the red oxide of iron that in said mixture, adds oxammonium hydrochloride weight;
(4), said mixture, under 90 ± 5 ℃, fully ground 4～5 hours, reduce to room temperature, the washing, the oven dry, the N-hydroxyphthalimide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101086656A CN101845012B (en) | 2010-02-10 | 2010-02-10 | Method for synthesizing N-hydroxy phthalimide with solid-phase process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101086656A CN101845012B (en) | 2010-02-10 | 2010-02-10 | Method for synthesizing N-hydroxy phthalimide with solid-phase process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101845012A CN101845012A (en) | 2010-09-29 |
| CN101845012B true CN101845012B (en) | 2012-03-21 |
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|---|---|---|---|
| CN2010101086656A Expired - Fee Related CN101845012B (en) | 2010-02-10 | 2010-02-10 | Method for synthesizing N-hydroxy phthalimide with solid-phase process |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040551B (en) * | 2010-10-11 | 2012-06-20 | 山东郁茏生物科技有限公司 | Synthesizing method of phthaloyl-beta-alanine |
| CN105111128B (en) * | 2015-09-14 | 2017-09-05 | 南京红宝丽醇胺化学有限公司 | A kind of preparation method of N hydroxyphthalimides |
| WO2017204935A1 (en) | 2016-05-26 | 2017-11-30 | Exxonmobil Chemical Patents Inc. | Production of cyclic imides suitable for oxidation catalysis |
| US11014883B2 (en) | 2016-05-26 | 2021-05-25 | 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 |
| CN108929246B (en) * | 2018-07-09 | 2021-07-02 | 湖南中医药大学 | Method for preparing hydroximic acid derivatives by solid-state method |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051170A (en) * | 1989-10-25 | 1991-05-08 | 国家医药管理局天津药物研究院 | The synthetic method of oxoamino-aliphatic carboxylic acid |
| 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 |
| CN101372473B (en) * | 2008-10-16 | 2011-11-02 | 复旦大学 | Preparation of N-hydroxy diimide |
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2010
- 2010-02-10 CN CN2010101086656A patent/CN101845012B/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| CN101845012A (en) | 2010-09-29 |
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| CB03 | Change of inventor or designer information |
Inventor after: Li Ruiju Inventor after: Chen Zilei Inventor after: Wang Fengen Inventor after: Fang Liping Inventor after: Dong Zhan Inventor before: Li Ruiju Inventor before: Chen Zilei Inventor before: Wang Fengen Inventor before: Fang Liping Inventor before: Dong Zhan |
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Owner name: JIANGSU CHENPAI PHARMACEUTICAL GROUP CO., LTD. Free format text: FORMER OWNER: LI RUIJU Effective date: 20130705 |
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Free format text: CORRECT: ADDRESS; FROM: 250100 JINAN, SHANDONG PROVINCE TO: 226100 NANTONG, JIANGSU PROVINCE |
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Effective date of registration: 20130705 Address after: 226100 No. 172, Renmin Middle Road, Haimen City, Jiangsu, Nantong Patentee after: JIANGSU CHENPAI PHARMACEUTICAL CO.,LTD. Address before: Mulberry road Licheng District 250100 in Shandong city of Ji'nan province No. 30 Patentee before: Li Ruiju |
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