CN107445897A - A kind of synthetic method of imidazolidine - Google Patents
A kind of synthetic method of imidazolidine Download PDFInfo
- Publication number
- CN107445897A CN107445897A CN201710515300.7A CN201710515300A CN107445897A CN 107445897 A CN107445897 A CN 107445897A CN 201710515300 A CN201710515300 A CN 201710515300A CN 107445897 A CN107445897 A CN 107445897A
- Authority
- CN
- China
- Prior art keywords
- imidazolidine
- added
- synthetic method
- sulfuric acid
- guanidine
- 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.)
- Pending
Links
- 0 CCN(CCN1)C1=* Chemical compound CCN(CCN1)C1=* 0.000 description 1
- JBGDUDIUIQVGCM-UHFFFAOYSA-N NCC(N)N[N+]([O-])=O Chemical compound NCC(N)N[N+]([O-])=O JBGDUDIUIQVGCM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/44—Nitrogen atoms not forming part of a nitro radical
- C07D233/52—Nitrogen atoms not forming part of a nitro radical with hetero atoms directly attached to said nitrogen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of synthetic method of imidazolidine, comprise the following steps：(1) concentrated sulfuric acid is added in 500mL round-bottomed flasks, guanidine nitrate, control system temperature≤40 DEG C are then added with 2~3g/min speed；(2) after the completion of guanidine nitrate feeds intake, 30~40min is incubated under≤40 DEG C of temperature hierarchies；(3) after insulation terminates, the material in step (2) is added ice solution is carried out in water ice solution, cooled, filtered, washing, obtain Intermediate nitro guanidine；(4) nitroguanidines of step (3), mass percentage concentration are sequentially added into reactor than sulfuric acid that the TBAB catalyst for 1%, mass concentration percentage are 70%, then ethylenediamine is added dropwise, and it is warming up to 80~90 DEG C of reactions, filtration washing is dried after the completion of reaction, obtains imidazolidine.The advantage of the invention is that：The present invention uses the less TBAB of toxicity to reduce the density of infection to health for catalyst, meanwhile, the synthetic method can improve the yield and purity of product.
Description
Technical field
The invention belongs to chemical field, more particularly to a kind of synthetic method of imidazolidine.
Background technology
In recent years with the agricultural chemicals such as imidacloprid, imidaclothiz international and domestic demand continuous increase so that intermediate
The demand of imidazolidine is also being continuously increased.Imidazolidine requires very strict during the course of the reaction, and production process controls bad, meeting
Cause the product quality of downstream product low.
Through retrieval, the A of patent CN 102558060 disclose a kind of preparation technology of imidazolidine, using by aqueous solvent, purity
Sulfuric acid that the ethylenediamine for being 99% for 98% cetyl trimethylammonium bromide catalyst, purity, concentration are 98%, quality contain
Nitroguanidine, the ammoniacal liquor of levels 20% of amount 90% are backed up by certain weight ratio, and imidazolidine then is made by following process：
Add water in reactor, put into cetyl trimethylammonium bromide catalyst, after dissolving, ethylenediamine is subsequently added into, with dense sulphur
Acid regulation pH value, while control temperature to be less than 80 DEG C, nitroguanidine is then added, pH value is adjusted between 8-8.5 with ammoniacal liquor, prepares miaow
Oxazolidine.The present invention, as catalyst, is improved main reaction speed, reduced due to nitro from cetyl trimethylammonium bromide
Guanidine decomposes the influence to product yield；Molar product high income, up to 87.2%；Product content >=99.0%；But the present invention's
The defects of certain be present in preparation method：Cetyl trimethylammonium bromide is high toxic material, to health in preparation process
It is unfavorable.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of synthetic method of imidazolidine, using the less tetrabutyl of toxicity
Ammonium bromide is catalyst, can reduce the density of infection to health, meanwhile, the synthetic method can improve product yield and
Purity.
In order to solve the above technical problems, the technical scheme is that：A kind of synthetic method of imidazolidine, its innovative point exist
In：The synthetic method comprises the following steps：
(1) concentrated sulfuric acid is added in 500mL round-bottomed flasks, guanidine nitrate, control volume are then added with 2~3g/min speed
It is temperature≤40 DEG C；
(2) after the completion of guanidine nitrate feeds intake, 30~40min is incubated under≤40 DEG C of temperature hierarchies；
(3) after insulation terminates, the material in step (2) is added ice solution is carried out in water ice solution, be cooled to 15~20 DEG C of mistakes
Filter, washing, obtains Intermediate nitro guanidine；
(4) nitroguanidines of step (3), mass percentage concentration are sequentially added into reactor than the tetrabutyl phosphonium bromide for 1%
Ammonium catalyst, the sulfuric acid that mass concentration percentage is 70%, are then added dropwise ethylenediamine, and are warming up to 80~90 DEG C of reactions, react
After the completion of filtration washing dry, obtain imidazolidine；Its specific reactions steps is as follows：
Further, the molal weight of guanidine nitrate and concentrated sulfuric acid ratio is 1 in the step (1):2.5.
Further, the dosage of water ice solution is 4 times of concentrated sulfuric acid dosage in step (1) in the step (3).
Further, nitroguanidine, ethylenediamine, the sulfuric acid mole matter that mass concentration percentage is 70% in the step (4)
Amount is than being 1:1:0.85.
Further, TBAB dosage is nitroguanidine, sulfuric acid and ethylenediamine in step (4) in the step (4)
The 1% of overall reaction liquid.
The advantage of the invention is that：
(1) synthetic method of imidazolidine of the present invention, product yield is made by adding phase transfer catalyst TBAB
Improve, product purity improves, and product content can be made to bring up to more than 99.5%, product yield brings up to more than 90.0%；Four fourths
It is small that base ammonium bromide is compared to other catalyst toxicities, is dissolved in water, and it is two-phase to control reaction, and phase transfer catalysis (PTC) effect is better than it
His catalyst, and then can also reduce the density of infection to health；
(2) synthetic method of imidazolidine of the present invention, the speed that control adds guanidine nitrate is to prevent reaction heat is excessive from leading
Cause slug, and control system temperature≤40 DEG C, be to prevent raw material decomposes, and 30~40min be incubated in the temperature hierarchy,
Dehydration can be caused to carry out complete, by strictly controlling each reaction condition technological parameter, further ensure that imidazolidine
The molar yield and purity of product..
Embodiment
The following examples can make professional and technical personnel that the present invention be more fully understood, but therefore not send out this
It is bright to be limited among described scope of embodiments.
Embodiment 1
The 220g concentrated sulfuric acids are added in 500ml round-bottomed flasks, 100g guanidine nitrates are added with 2g/min speed, control temperature
No more than 40 DEG C, guanidine nitrate is fed intake 30min, and after the end that feeds intake, 40 DEG C of insulation 30min, feed liquid is added in 880g water ice solutions, cooling
To 15 DEG C of filterings, washing, intermediate product nitroguanidine is obtained.
125g nitroguanidines are sequentially added in 500ml four-hole boiling flasks, the sulfuric acid that 50g mass concentrations percentage is 70%,
0.2g TBABs, ethylenediamine 32g is added dropwise, is warming up to 80 DEG C of reactions, filtration washing dries to obtain after the completion of sampling reaction
Faint yellow solid imidazolidine 60g.
The content of imidazolidine is 98.5% in the present embodiment, yield 90.9%.
Embodiment 2
The 220g concentrated sulfuric acids are added in 500ml round-bottomed flasks, 100g guanidine nitrates are added with 3g/min speed, control temperature
No more than 40 DEG C, guanidine nitrate feeds intake 30min, and guanidine nitrate feeds intake after end, and 40 DEG C of insulation 40min, feed liquid adds 880g water ice solutions
In, 20 DEG C of filterings are cooled to, washes, obtains intermediate product nitroguanidine.
125g nitroguanidines are sequentially added in 500ml four-hole boiling flasks, the sulfuric acid that 50g mass concentrations percentage is 70%,
0.2g TBABs, ethylenediamine 32g is added dropwise, is warming up to 90 DEG C of reactions, filtration washing dries to obtain after the completion of sampling reaction
Faint yellow solid imidazolidine 60.2g.
The content of imidazolidine is 98.4% in the present embodiment, yield 91.1%.
Embodiment 3
The 220g concentrated sulfuric acids are added in 500ml round-bottomed flasks, 100g guanidine nitrates are added with 2g/min speed, control temperature
No more than 40 DEG C, guanidine nitrate feeds intake 30min, and guanidine nitrate feeds intake after end, and 40 DEG C of insulation 35min, feed liquid adds 880g water ice solutions
In, 15 DEG C of filterings are cooled to, washes, obtains intermediate product nitroguanidine.
125g nitroguanidines are sequentially added in 500ml four-hole boiling flasks, the sulfuric acid that 50g mass concentrations percentage is 70%,
0.2g TBABs, ethylenediamine 32g is added dropwise, is warming up to 80 DEG C of reactions, filtration washing dries to obtain after the completion of sampling reaction
Faint yellow solid imidazolidine 59.5g.
The content of imidazolidine is 98.3% in the present embodiment, yield 90.0%.
The general principle and principal character and advantages of the present invention of the present invention has been shown and described above.The skill of the industry
For art personnel it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification is explanation
The principle of the present invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these
Changes and improvements all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and
Its equivalent thereof.
Claims (5)
- A kind of 1. synthetic method of imidazolidine, it is characterised in that：The synthetic method comprises the following steps：(1) concentrated sulfuric acid is added in 500mL round-bottomed flasks, guanidine nitrate, control system temperature are then added with 2~3g/min speed ≤ 40 DEG C of degree；(2) after the completion of guanidine nitrate feeds intake, 30~40min is incubated under≤40 DEG C of temperature hierarchies；(3) after insulation terminates, the material in step (2) is added ice solution is carried out in water ice solution, be cooled to 15~20 DEG C of filterings, water Wash, obtain Intermediate nitro guanidine；(4) nitroguanidines of step (3), mass percentage concentration are sequentially added into reactor than being urged for 1% TBAB Agent, the sulfuric acid that mass concentration percentage is 70%, are then added dropwise ethylenediamine, and are warming up to 80~90 DEG C of reactions, and reaction is completed Filtration washing is dried afterwards, obtains imidazolidine；Its specific reactions steps is as follows：
- 2. the synthetic method of imidazolidine according to claim 1, it is characterised in that：In the step (1) guanidine nitrate with it is dense The molal weight ratio of sulfuric acid is 1:2.5.
- 3. the synthetic method of imidazolidine according to claim 1, it is characterised in that：The use of water ice solution in the step (3) Measure as 4 times of concentrated sulfuric acid dosage in step (1).
- 4. the synthetic method of imidazolidine according to claim 1, it is characterised in that：Nitroguanidine, second two in the step (4) The sulfuric acid molal weight ratio that amine, mass concentration percentage are 70% is 1:1:0.85.
- 5. the synthetic method of imidazolidine according to claim 1, it is characterised in that：Tetrabutyl phosphonium bromide in the step (4) Ammonium dosage is the 1% of nitroguanidine in step (4), sulfuric acid and ethylenediamine overall reaction liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710515300.7A CN107445897A (en) | 2017-06-29 | 2017-06-29 | A kind of synthetic method of imidazolidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710515300.7A CN107445897A (en) | 2017-06-29 | 2017-06-29 | A kind of synthetic method of imidazolidine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107445897A true CN107445897A (en) | 2017-12-08 |
Family
ID=60488442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710515300.7A Pending CN107445897A (en) | 2017-06-29 | 2017-06-29 | A kind of synthetic method of imidazolidine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107445897A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020058807A1 (en) * | 2018-09-17 | 2020-03-26 | Upl Ltd | A manufacturing process for 2-nitroimino heterocyclic compounds |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558060A (en) * | 2011-12-29 | 2012-07-11 | 南通天泽化工有限公司 | Process for preparing imidazolidine |
| CN105924428A (en) * | 2016-06-29 | 2016-09-07 | 南通天泽化工有限公司 | Method for synthesizing imidacloprid |
-
2017
- 2017-06-29 CN CN201710515300.7A patent/CN107445897A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558060A (en) * | 2011-12-29 | 2012-07-11 | 南通天泽化工有限公司 | Process for preparing imidazolidine |
| CN105924428A (en) * | 2016-06-29 | 2016-09-07 | 南通天泽化工有限公司 | Method for synthesizing imidacloprid |
Non-Patent Citations (1)
| Title |
|---|
| 潘英明等: "新型杀虫剂取代-2-硝基亚氨基-咪唑烷的合成及初步药效试验", 《农药》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020058807A1 (en) * | 2018-09-17 | 2020-03-26 | Upl Ltd | A manufacturing process for 2-nitroimino heterocyclic compounds |
| CN112996775A (en) * | 2018-09-17 | 2021-06-18 | Upl有限公司 | Process for preparing 2-nitroiminoheterocycles |
| US11440890B2 (en) | 2018-09-17 | 2022-09-13 | Upl Ltd. | Manufacturing process for 2-nitroimino heterocyclic compounds |
| CN112996775B (en) * | 2018-09-17 | 2023-09-19 | Upl有限公司 | Process for preparing 2-nitroiminoheterocyclic compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103073438B (en) | Ambroxol hydrochloride compound refining method | |
| CN107235814A (en) | It is a kind of for slow-release fertilizer of planting fruit trees and preparation method thereof | |
| CN107445897A (en) | A kind of synthetic method of imidazolidine | |
| CN109420502A (en) | A kind of preparation method of heat-resisting copper-zinc-based catalyst | |
| CN107235970A (en) | A kind of synthetic method of imidaclothiz | |
| CN108187680A (en) | A kind of preparation method of alcohol dehydrogenase ammonification synthesis acetonitrile catalyst | |
| CN105037186A (en) | Preparation method of aminomethylbenzoic acid | |
| CN106831517A (en) | A kind of synthetic method of thiocarbohydrazide | |
| CN105037073B (en) | A kind of synthetic method of biaryl compounds | |
| CN104829416B (en) | A continuous production process of chloroethane | |
| CN106810546A (en) | A kind of umeclidinium compound | |
| CN111217756B (en) | Preparation method of dexmedetomidine hydrochloride | |
| CN105481740B (en) | The preparation method of isothiocyano methyl formate | |
| CN110878023B (en) | Clean production method for preparing 2, 5-dichloronitrobenzene by continuous nitration | |
| CN110590591B (en) | Preparation method of iodixanol and iohexol impurities | |
| CN106631850A (en) | Post-treatment process for synthesis of p-hydroxyphenylglycine | |
| CN102399173B (en) | Method for preparing biurea | |
| CN112851554A (en) | Preparation method of guanidine nitrate | |
| CN107573301B (en) | Preparation method of tricyclazole intermediate | |
| CN111808018A (en) | Production process of acetamiprid | |
| CN105272908B (en) | A kind of synthesis technology of 3- hydroxyls -2- nitropyridines | |
| CN107235993A (en) | A kind of preparation method of cycloxaprid | |
| CN110790685A (en) | Method for producing urea phosphate by wet-process phosphoric acid reduced pressure evaporation coupled elution crystallization | |
| CN109134473A (en) | A kind of preparation method of the sweet guanidine of dinitro | |
| CN103130247A (en) | Process for producing ammonium sulfate and hydrogen chloride by employing ammonium chloride and sulfuric acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20171208 |
|
| RJ01 | Rejection of invention patent application after publication |