CN104387313A - Preparation method of 1,2-cyclopentadicarboximide - Google Patents
Preparation method of 1,2-cyclopentadicarboximide Download PDFInfo
- Publication number
- CN104387313A CN104387313A CN201410594596.2A CN201410594596A CN104387313A CN 104387313 A CN104387313 A CN 104387313A CN 201410594596 A CN201410594596 A CN 201410594596A CN 104387313 A CN104387313 A CN 104387313A
- Authority
- CN
- China
- Prior art keywords
- ring penta
- dicarboximide
- preparation
- diformamide
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 0 C[C@@](CC1C(*)=O)CC1C(NC(C1*(*)CCC1)=O)=O Chemical compound C[C@@](CC1C(*)=O)CC1C(NC(C1*(*)CCC1)=O)=O 0.000 description 2
- MLNHEBAJXZVWER-UHFFFAOYSA-N NC(C(CCC1)C1C(N)=O)=O Chemical compound NC(C(CCC1)C1C(N)=O)=O MLNHEBAJXZVWER-UHFFFAOYSA-N 0.000 description 1
- QCWDCTDYSDJKTP-UHFFFAOYSA-N O=C(C1C2CCC1)NC2=O Chemical compound O=C(C1C2CCC1)NC2=O QCWDCTDYSDJKTP-UHFFFAOYSA-N 0.000 description 1
- ASJCSAKCMTWGAH-UHFFFAOYSA-N OC(C(CCC1)C1C(O)=O)=O Chemical compound OC(C(CCC1)C1C(O)=O)=O ASJCSAKCMTWGAH-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/52—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring condensed with a ring other than six-membered
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to an organic synthesis method and particularly relates to a preparation method of 1,2-cyclopentadicarboximide. The preparation method comprises the following steps of in the presence of 1,2-cyclopentadicarboxylic acid serving as a catalyst, carrying out cyclization on 1,2-cyclopentadicarboxamide to prepare 1,2-cyclopentadicarboximide; adding an appropriate amount of depolymerizing agent into a reaction solution so that a part of a byproduct is also depolymerized into a target product and carrying out reduced pressure distillation to obtain crude 1,2-cyclopentadicarboximide; finally refining and reshaping with an organic solvent to obtain 1,2-cyclopentadicarboximid finished product. By the preparation method, the process route is simplified, the reaction conditions are improved, the quality and yield of the product are improved; furthermore, a large amount of waste salt pollution in the conventional process is eliminated, the produced ammonia can be recycled and the preparation method is an environmental-friendly feasible route for industrial production.
Description
Technical field
The present invention relates to a kind of preparation method of 1,2-ring penta dicarboximide, belong to the field of chemical synthesis.
Background technology
The method of existing synthesis 1,2-ring penta dicarboximide has following several:
With 1,2-ring penta diformamide directly Reactive Synthesis 1,2-ring penta dicarboximide under 300 DEG C of high temperature.This technological reaction temperature is high, and coking phenomenon is serious, and product yield low (less than 50%), of poor quality, there is the risk of punching material simultaneously.Reaction formula is as follows:
About how reducing temperature of reaction, reducing the problem of coking, people propose different solutions.Patent ZL200510049977.3 propose with 1,2-ring penta diformamide in organic solvent with sour salify, then cyclization obtain 1,2-ring penta dicarboximide, reaction formula is as follows:
ZL201110248438.8 provides a similar scheme, with pentamethylene-1-methane amide-2-ammonium formiate for raw material, through phosphoric acid hydrolysis, after without separation direct cyclization become 1,2-ring penta dicarboximide.Reaction formula is as follows:
Although above-mentioned two methods all reduce temperature of reaction (220 ~ 260 DEG C), improve yield (yield > 80%), all produce a large amount of abraum salts, so Atom economy is not high.Moreover ring-closure reaction carries out under strong acid, not only serious to equipment corrosion, and the partial hydrolysis of acid amides can be caused, thus yield is not too desirable with quality.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of environmental friendliness, method that simple process, high yield, high quality, low cost prepare 1,2-ring penta dicarboximide.
Present invention employs following technical scheme: add 1,2-ring penta diformamide (wetting) and proper catalyst 1,2-ring penta dioctyl phthalate in container, heat temperature raising, 220 ~ 240 DEG C of insulations 1 ~ 4 hour, cyclization obtained 1,2-ring penta dicarboximide.Meanwhile, the ammonia Water spray that reaction produces absorbs into ammoniacal liquor, recycles.Then above-mentioned reaction solution is added appropriate depolymerizing agent, make part by-product also be depolymerized to target product, underpressure distillation, obtain 1,2-ring penta dicarboximide crude product, content in crude product can reach 99.5%.Finally by organic solvent refining reformed shape, obtain 1,2-ring penta dicarboximide finished product.Yield more than 90%, content can reach 99.7%.
Reaction equation
Main reaction is:
Side reaction (one):
It is obtained that the present invention's 1,2-ring penta dioctyl phthalate used can pass easily through the hydrolysis of 1,2-ring penta diformamide, and reaction formula is as follows:
Feature of the present invention is: 1. prepare in the process of 1,2-ring penta dicarboximide, with 1,2-ring penta dioctyl phthalate is that catalyzer not only can accelerate ring-closure reaction speed, and can form congruent melting with 1,2-ring penta diformamide, reduction system viscosity, reduces burnt material and produces.2. directly feed intake by 1,2-ring penta diformamide wet product, reaction system can be made moisture, prevent oxidation, decrease coking, reduce punching material risk.3. add depolymerizing agent underpressure distillation after reacting completely, improve yield and the quality of product.4. pair ammonia Water Sproading produced, can reduce three waste discharge.
In a word: the present invention not only simplifies processing route, improve reaction conditions, decrease coking and produce, improve quality product and yield, the ammonia simultaneously produced achieves recycle.For suitability for industrialized production provides the feasible scheme of a green.
Embodiment
Below in conjunction with specific embodiment, the present invention is made a detailed explanation.
Embodiment 1
1,2-ring penta dioctyl phthalate 8g (giving money as a gift) is dropped into, 1 in 500ml four-hole bottle, 2-ring penta diformamide is 160g (meter of giving money as a gift altogether, wherein moisture 10.8%), be warmed up to 220 DEG C, between 220 ~ 240 DEG C, be incubated 2 hours, obtain 1,2-ring penta dicarboximide reaction solution, then add ammonium metaphosphate 0.5g, underpressure distillation, obtain 1,2-ring penta dicarboximide crude product.Add toluene again to dissolve, cooling, crystallization, filters, dry 1,2-ring penta dicarboximide fine work (mother liquor can directly be applied mechanically), obtain 136.1g, yield is (with 1,2-ring penta dioctyl phthalate is with 1,2-ring penta diformamide total mole number meter) be 92.0%, content is 99.85%, fusing point 85.3 ~ 86.1 DEG C.Quality reaches gliclazide levels necessitate.
Embodiment 2
1,2-ring penta dioctyl phthalate 8g (giving money as a gift) is dropped into, 1 in 500ml four-hole bottle, 2-ring penta diformamide is 160g (meter of giving money as a gift altogether, wherein moisture 10.8%), be warmed up to 220 DEG C, between 220 ~ 240 DEG C, be incubated 2 hours, obtain 1,2-ring penta dicarboximide reaction solution, does not add depolymerizing agent, underpressure distillation, obtain 1,2-ring penta dicarboximide crude product.Add toluene again to dissolve, cooling, crystallization, filter, dry 1,2-ring penta dicarboximide fine work, obtain 112.6g, yield is (with 1,2-ring penta dioctyl phthalate is with 1,2-ring penta diformamide total mole number meter) be 76.1%, content is 99.1%, fusing point 84.2 ~ 85.2 DEG C.
Embodiment 3
1,2-ring penta dioctyl phthalate 8g (giving money as a gift) is dropped into, 1 in 500ml four-hole bottle, 2-ring penta diformamide is 160g (meter of giving money as a gift altogether, wherein moisture 10.8%), be warmed up to 220 DEG C, between 220 ~ 240 DEG C, be incubated 2 hours, obtain 1,2-ring penta dicarboximide reaction solution, then add primary ammonium phosphate 0.5g, underpressure distillation, obtain 1,2-ring penta dicarboximide crude product.Add toluene again to dissolve, cooling, crystallization, filter, dry 1,2-ring penta dicarboximide fine work, obtain 119.1g, yield is (with 1,2-ring penta dioctyl phthalate is with 1,2-ring penta diformamide total mole number meter) be 80.5%, content is 99.45%, fusing point 85.0 ~ 86.2 DEG C.
Embodiment 4
1,2-ring penta dioctyl phthalate 8g (giving money as a gift) is dropped into, 1 in 500ml four-hole bottle, 2-ring penta diformamide is 160g (meter of giving money as a gift altogether, wherein moisture 10.8%), be warmed up to 220 DEG C, between 220 ~ 240 DEG C, be incubated 2 hours, obtain 1,2-ring penta dicarboximide reaction solution, then add Secondary ammonium phosphate 0.5g, underpressure distillation, obtain 1,2-ring penta dicarboximide crude product.Add toluene again to dissolve, cooling, crystallization, filter, dry 1,2-ring penta dicarboximide fine work, obtain 120.1g, yield is (with 1,2-ring penta dioctyl phthalate is with 1,2-ring penta diformamide total mole number meter) be 81.2%, content is 99.75%, fusing point 85.4 ~ 86.6 DEG C.Quality reaches gliclazide levels necessitate.
Embodiment 5
1,2-ring penta dioctyl phthalate 8g (giving money as a gift) is dropped into, 1 in 500ml four-hole bottle, 2-ring penta diformamide is 160g (meter of giving money as a gift altogether, wherein moisture 10.8%), be warmed up to 220 DEG C, between 220 ~ 240 DEG C, be incubated 2 hours, obtain 1,2-ring penta dicarboximide reaction solution, then add ammonium phosphite 0.5g, underpressure distillation, obtain 1,2-ring penta dicarboximide crude product.Add toluene again to dissolve, cooling, crystallization, filter, dry 1,2-ring penta dicarboximide fine work, obtain 132.5g, yield is (with 1,2-ring penta dioctyl phthalate is with 1,2-ring penta diformamide total mole number meter) be 89.6%, content is 99.78%, fusing point 85.7 ~ 86.9 DEG C.Quality reaches gliclazide levels necessitate.
Claims (10)
1. a preparation method for 2-ring penta dicarboximide, this preparation method comprises the following steps:
A) first add 1,2-ring penta diformamide and proper catalyst 1,2-ring penta dioctyl phthalate in container, heating, then be incubated cyclization at moderate temperatures, obtained 1,2-ring penta dicarboximide; The ammonia Water spray that reaction produces absorbs into ammoniacal liquor, recycles;
B) above-mentioned reaction solution is added appropriate depolymerizing agent, make part by-product also be depolymerized to target product, underpressure distillation obtains 1,2-ring penta dicarboximide crude product, then through organic solvent refining reformed shape, obtains 1,2-ring penta dicarboximide finished product.
2. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that the catalyzer 1 a) described in step, 2-ring penta dioctyl phthalate and 1, the mol ratio of 2-ring penta diformamide is 1: 10 ~ 100, preferably 1: 14 ~ 30, most preferably 1: 20.
3. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that 1,2-ring penta diformamide a) described in step is wet product, water content between 1 ~ 40%, preferably 5 ~ 20%, most preferably 10 ~ 15%.
4. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that holding temperature a) described in step is 220 ~ 240 DEG C; Soaking time is 1 ~ 4 hour, preferably 2 ~ 2.5 hours.
5. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that the ammonia that reaction a) described in step produces absorbs into ammoniacal liquor, recycles.
6. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that depolymerizing agent b) described in step is phosphorous ammonium salt, is preferably ammonium metaphosphate, Secondary ammonium phosphate, primary ammonium phosphate, ammonium phosphite, most preferably ammonium metaphosphate.
7. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that the mol ratio of depolymerizing agent b) described in step and 1,2-ring penta diformamide is 1: 100 ~ 1000, most preferably 1: 200.
8. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that 1,2-ring penta diformamide crude product b) described in step is that underpressure distillation obtains.
9. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that depolymerization b) described in step occurs with underpressure distillation simultaneously.
10. the preparation method of 1,2-ring penta dicarboximide as claimed in claim 1, is characterized in that organic solvent nail benzene b) described in step, dimethylbenzene, organic solvent act as refining reformed shape, mother liquor can time use.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410594596.2A CN104387313B (en) | 2014-10-22 | 2014-10-22 | A kind of preparation method of 1,2-ring penta dicarboximide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410594596.2A CN104387313B (en) | 2014-10-22 | 2014-10-22 | A kind of preparation method of 1,2-ring penta dicarboximide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104387313A true CN104387313A (en) | 2015-03-04 |
| CN104387313B CN104387313B (en) | 2015-12-30 |
Family
ID=52605291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410594596.2A Active CN104387313B (en) | 2014-10-22 | 2014-10-22 | A kind of preparation method of 1,2-ring penta dicarboximide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104387313B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569994A (en) * | 2018-06-01 | 2018-09-25 | 滨海博大化工有限公司 | The synthetic method of 1,2- of one kind rings, penta dicarboximide |
| CN109206358A (en) * | 2018-09-14 | 2019-01-15 | 济南爱思医药科技有限公司 | The synthetic method of 1,2- of one kind ring, penta dicarboximide |
| CN112624958A (en) * | 2020-12-30 | 2021-04-09 | 安徽金鼎医药股份有限公司 | Synthetic method of medical intermediate 1, 2-cyclopentadienimide |
| CN115232058A (en) * | 2022-08-01 | 2022-10-25 | 上海巽田科技股份有限公司 | Synthesis method of gliclazide intermediate 1,2-cyclopentanedicarboxamide |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314340A (en) * | 2000-03-21 | 2001-09-26 | 山东省医药工业研究所 | Method for preparing cyclopentane imide |
| CN1692772A (en) * | 2005-06-20 | 2005-11-09 | 余内逊 | Method for preparing milk powder contg. micron sang, white fungus and oligose for face-beauty, toning-lungs and lowering blood-sugar |
| CN1876636A (en) * | 2005-06-07 | 2006-12-13 | 台州市四维化工厂 | Cyclopentane1,2-diimide preparation method |
| CN102816102A (en) * | 2011-06-08 | 2012-12-12 | 瑟维尔实验室 | Synthesis process, and crystalline form of 4-{3-[cis-hexahydrocyclopenta[c]pyrrol-2(1H)-yl]propoxy} benzamide hydrochloride and pharmaceutical compositions containing it |
| CN102952063A (en) * | 2011-08-26 | 2013-03-06 | 山东方明药业集团股份有限公司 | Synthesis method for cyclopentane-1,2-dicarboximide |
-
2014
- 2014-10-22 CN CN201410594596.2A patent/CN104387313B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1314340A (en) * | 2000-03-21 | 2001-09-26 | 山东省医药工业研究所 | Method for preparing cyclopentane imide |
| CN1876636A (en) * | 2005-06-07 | 2006-12-13 | 台州市四维化工厂 | Cyclopentane1,2-diimide preparation method |
| CN1692772A (en) * | 2005-06-20 | 2005-11-09 | 余内逊 | Method for preparing milk powder contg. micron sang, white fungus and oligose for face-beauty, toning-lungs and lowering blood-sugar |
| CN102816102A (en) * | 2011-06-08 | 2012-12-12 | 瑟维尔实验室 | Synthesis process, and crystalline form of 4-{3-[cis-hexahydrocyclopenta[c]pyrrol-2(1H)-yl]propoxy} benzamide hydrochloride and pharmaceutical compositions containing it |
| CN102952063A (en) * | 2011-08-26 | 2013-03-06 | 山东方明药业集团股份有限公司 | Synthesis method for cyclopentane-1,2-dicarboximide |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108569994A (en) * | 2018-06-01 | 2018-09-25 | 滨海博大化工有限公司 | The synthetic method of 1,2- of one kind rings, penta dicarboximide |
| CN109206358A (en) * | 2018-09-14 | 2019-01-15 | 济南爱思医药科技有限公司 | The synthetic method of 1,2- of one kind ring, penta dicarboximide |
| CN109206358B (en) * | 2018-09-14 | 2021-10-29 | 济南爱思医药科技有限公司 | Synthesis method of 1, 2-cyclopentadiimide |
| CN112624958A (en) * | 2020-12-30 | 2021-04-09 | 安徽金鼎医药股份有限公司 | Synthetic method of medical intermediate 1, 2-cyclopentadienimide |
| CN115232058A (en) * | 2022-08-01 | 2022-10-25 | 上海巽田科技股份有限公司 | Synthesis method of gliclazide intermediate 1,2-cyclopentanedicarboxamide |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104387313B (en) | 2015-12-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104387313B (en) | A kind of preparation method of 1,2-ring penta dicarboximide | |
| CN106380425A (en) | Production process of N-(N-cyclohexylamide-N', N'-dmethyl amidine)-N-methyl ethyl carbamate | |
| CN103936759B (en) | (3aS, 6aR)-1,3-dibenzyl-tetrahydrochysene-4H-thieno-[3,4-d] imidazoles-2,4-(1H) simple and convenient process for preparing of-diketone | |
| CN103951591B (en) | A kind of guanidine hydrochloride production technology | |
| CN106008262A (en) | Preparation method of 4,5-dicyan base-2-trifluoro-methylimidazole and prepared intermediate and salt thereof | |
| CN105399767A (en) | Production method of N-alkyl substituted phosphoric triamide | |
| CN102030711A (en) | Synthesis method of 2-imidazolidinone | |
| CN112321561A (en) | Method for preparing 1, 3-propane sultone from 3-hydroxypropanesulfonic acid | |
| CN109206343A (en) | A kind of preparation method of adiponitrile | |
| CN103073458A (en) | Method for recovering trifluoromethanesulfonic acid in wastewater | |
| CN108164514B (en) | Preparation method of epoxiconazole | |
| CN108299245B (en) | Synthesis process of N, N' -bis (3-dimethylaminopropyl) urea | |
| KR20100118747A (en) | Improved preparation method of sarpogrelate hydrochloride | |
| CN109574893A (en) | A kind of method of sodium thiocarbonate synthesis mercaptoethylamine hydrochloride | |
| CN101565428A (en) | Preparation method of prulifloxacin | |
| CN104876889A (en) | A synthesis method of a compound | |
| CN110590702B (en) | Novel method for preparing 2-mercaptobenzothiazole | |
| CN107129446A (en) | The technique of sulfate ion is reduced in a kind of methyl propane sulfonic acid building-up process of 2 acrylamido 2 | |
| CN109836344B (en) | Method for producing glycine by organic solvent | |
| CN105460909B (en) | The post-processing approach of hydroxylamine hydrochloride mother liquid recovery process | |
| JP2010111665A (en) | Method of producing 2-hydroxy-4-methylthiobutanoic acid | |
| CN108610288B (en) | Preparation method and purification method of 5-chloro-8-hydroxyquinoline | |
| CN102408374A (en) | Synthesis method of 1-methylsulfonyl 2-imidazolidinone | |
| WO2015012271A1 (en) | Method for producing heterocyclic compound | |
| CN108752271A (en) | A kind of synthetic method of oxyquinoline |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20200331 Address after: 016041 Lianxin Road, industrial park, Wuda District, Wuhai City, Inner Mongolia Autonomous Region (east side of Yiyang company) Patentee after: INNER MONGOLIA YUANHONG FINE CHEMICAL Co.,Ltd. Address before: 224555 Jiangsu province Yancheng City Binhai Industrial Zone head Zeng Patentee before: BINHAI BODA CHEMICAL Co.,Ltd. |
|
| TR01 | Transfer of patent right |