CN101274904B - Preparation for 3, 4-dichloro phenyl isocyanate - Google Patents
Preparation for 3, 4-dichloro phenyl isocyanate Download PDFInfo
- Publication number
- CN101274904B CN101274904B CN200810025438XA CN200810025438A CN101274904B CN 101274904 B CN101274904 B CN 101274904B CN 200810025438X A CN200810025438X A CN 200810025438XA CN 200810025438 A CN200810025438 A CN 200810025438A CN 101274904 B CN101274904 B CN 101274904B
- Authority
- CN
- China
- Prior art keywords
- phosgene
- dichloro
- dichlorphenamide bulk
- phenylcarbimide
- bulk powder
- 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.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing 3, 4-dichloro phenyl isocyanate. The method takes 3, 4-dichloroaniline as raw material and xylene, or benzene chloride, o (p) dichlorobenzene and other organic solvents which do not react chemically with phosgene as a reaction solvent, goes through two steps of phosgenation reaction under low temperature and high temperature and distillation to obtain products with purity over 98 percent. The technique of two steps of phosgenation reaction under low temperature and high temperature can effectively reduce side reaction and improve reaction efficiency; the total yield of the invention achieves over 97 percent calculated by 3, 4-dichloroaniline.
Description
Technical field
The present invention relates to a kind of synthetic method of organic compound, be specifically related to a kind of 3, the preparation method of 4-dichloro phenylcarbimide.
Background technology
3, and 4-dichloro phenylcarbimide (3,4-DCPI) be mainly used in synthetic and some the medical synthetic intermediate of agricultural chemicals such as carbamide herbicides (as Diuron Tech, methoxydiuron, neburon, swep), sterilant rice fourth FF.
3,4-dichloro phenylcarbimide is a white solid, and pungent odour is arranged, and is soluble in organic solvents such as toluene, dimethylbenzene, normal butane, and it is acid that the aqueous solution is.Be a kind of important organic intermediate, can be used for medicine, pesticide intermediate.Traditional technology is with 3,4-dichlorphenamide bulk powder, orthodichlorobenzene add in the reactor, and under agitation logical exsiccant hydrogen chloride gas feeds phosgene at 110～160 ℃ then until saturated, or single stage method directly feeds phosgene, fed phosgene again 20～30 minutes to solution becomes after clear, logical finishing, rectifying makes elaboration 3,4-dichloro phenylcarbimide, this method product content is low, and yield is low, generally is not more than 80%.
Summary of the invention
The purpose of this invention is to provide 3 of a kind of high yield, the preparation method of 4-dichloro phenylcarbimide elaboration.
For achieving the above object, the present invention the technical scheme that adopted as follows:
A kind of 3, the preparation method of 4-dichloro phenylcarbimide may further comprise the steps:
1, with 3, the 4-dichlorphenamide bulk powder is dissolved in the organic solvent, and 3, the amount of 4-dichlorphenamide bulk powder is 10～55% of an organic solvent weight, preferred 12～30%;
2, in reactor, add weight and be 3, the organic solvent of 3～15 times of 4-dichlorphenamide bulk powders, feeding weight is 3, the phosgene of 4-dichlorphenamide bulk powder 18～30%;
3,, slowly drip 3 of step (1) preparation, 4-dichlorphenamide bulk powder solution to reactor at-10～0 ℃;
4, drip after, stirring reaction 1～5 hour, the heat-up rate with 5～20 ℃/h is warming up to 110～150 ℃ again;
When 5, temperature is increased to 110～150 ℃, feed phosgene, be as clear as crystal state until material to reactor;
6, stop logical phosgene, catch up with phosgene 1～5h with rare gas element;
7, rectifying obtains 3 after removing solvent, 4-dichloro phenylcarbimide elaboration;
8, the back light gasification reaction kettle is applied mechanically after the solvent treatment.
Wherein, the organic solvent described in step 1 and the step 2 be not with the organic solvent of phosgene generation chemical reaction, preferred toluene, dimethylbenzene, Benzene Chloride, orthodichlorobenzene or santochlor.And the organic solvent in step 1 and the step 2 can be the same or different.
Wherein, rare gas element described in the step 6 is N
2
Wherein, but tail gas emptying up to standard after reclaiming phosgene.
Principle of the present invention is: 3, the 4-dichlorphenamide bulk powder can (hydrogenchloride be 3 with phosgene, hydrogenchloride, the by product that 4-dichlorphenamide bulk powder and phosgene reaction produce) reaction generates acyl chlorides and 3 respectively, the hydrochloride of 4-dichlorphenamide bulk powder is also emitted heat, decompose under the acyl chlorides hot conditions and generate 3,4-dichloro phenylcarbimide; 3, the hydrochloride of 4-dichlorphenamide bulk powder decomposes the back under hot conditions is badly in need of generating 3,4-dichloro phenylcarbimide with phosgene reaction.The principal reaction equation is as follows:
3,4-dichlorphenamide bulk powder and 3, the chemical property of 4-dichloro phenylcarbimide is all relatively more active, has side reaction in the reaction, and wherein main side reaction is: 3,4-dichloro phenylcarbimide is with excessive 3,4-dichlorphenamide bulk powder reaction generation ureas by product.
3,4-dichlorphenamide bulk powder and phosgene and hcl reaction generate acyl chlorides and hydrochloride respectively, two all a large amount of heat releases of reaction, keep lower temperature, adopting solution reaction is that reaction medium in time shifts out reaction heat with the dimethylbenzene equal solvent, can reduce side reaction effectively and take place, and guarantees that reacting balance carries out.
Reaction intermediate 3,4-dichlorphenamide bulk powder acyl chlorides, 3,4-dichlorphenamide bulk powder hydrochloride decomposes generation 3, during 4-dichloro phenylcarbimide, need provide enough heat energy, guarantee that intermediate product keeps in mind target product and transform, adopt higher temperature, can effectively improve conversion rate of products.
The present invention compared with prior art, its remarkable advantage is:
1, is that solvent in time shifts out reaction heat with dimethylbenzene etc., can reduces the generation of side reaction effectively.
2, adopt low temperature, two step of high temperature phosgenation reaction, 3,4-dichlorphenamide bulk powder and phosgene and hcl reaction generate acyl chlorides and hydrochloride respectively, two all a large amount of heat releases of reaction, keep lower temperature, adopting solution reaction is that reaction medium in time shifts out reaction heat with the dimethylbenzene equal solvent, can reduce side reaction effectively and take place, and guarantees that reacting balance carries out; The reaction intermediate acyl chlorides, when hydrochloride resolves into isocyanic ester, need provide enough heat energy, guarantee that intermediate product transforms to target product, adopt higher temperature of reaction, conversion rate of products can be provided effectively.
3, phosgene is excessive, reclaims, and can effectively improve 3, the transformation efficiency of 4-dichlorphenamide bulk powder.
4, reuse after the solvent treatment can effectively reduce the generation of side reaction.
5, by 3 of the inventive method preparation, 4-dichloro phenylcarbimide purity is more than 98%, and total recovery reaches (with 3,4-dichlorphenamide bulk powder meter) more than 97%.
Embodiment:
The invention will be further described below in conjunction with embodiment.
Embodiment 1:
In the 500L dissolution kettle, add 100 kilograms of dimethylbenzene, add 3,50 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 40 ℃, restir 30 minutes to 1 hour, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 215 kilograms of dimethylbenzene, cooling simultaneously feeds 10 kilograms of phosgene by the phosgene ingress pipe, when treating that temperature is reduced to-5 ℃, begin to drip 3,4-dichlorphenamide bulk powder solution is after dripping off in 2 hours, restir 1.5 hours, be warming up to 130 ℃ with 20 ℃/hour heat-up rates, the restock phosgene stops logical phosgene to material clear state, catch up with phosgene 1h with nitrogen, rectifying gets 56.6 kilograms of pure product, and product purity is 98.5%, with 3,4-dichlorphenamide bulk powder meter, 3,4-dichloro phenylcarbimide total recovery 97%, the back light gasification reaction kettle recycles after the solvent treatment.
Embodiment 2:
In the 500L dissolution kettle, add 110 kilograms of Benzene Chloride, add 3,55 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 50 ℃, restir 30 minutes to 1 hour, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 240 kilograms of Benzene Chloride, cooling simultaneously feeds 10 kilograms of phosgene by the phosgene ingress pipe, when treating that temperature is reduced to-5 ℃, begin to drip 3,4-dichlorphenamide bulk powder solution is after dripping off in 1.8 hours, restir 1.5 hours, be warming up to 125 ℃ with 20 ℃/hour heat-up rates, the restock phosgene stops logical phosgene to material clear state, catch up with phosgene 1h with nitrogen, rectifying gets 62.3 kilograms of pure product, and product purity is 98.7%, with 3,4-dichlorphenamide bulk powder meter, 3,4-dichloro phenylcarbimide total recovery 97.3%, the back light gasification reaction kettle recycles after the solvent treatment.
Embodiment 3:
In the 500L dissolution kettle, add the orthodichlorobenzene 120 kg, add 3,60 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 55 ℃, restir 30 minutes to 1 hour, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 250 kilograms of orthodichlorobenzenes, cooling simultaneously feeds 12 kilograms of phosgene by the phosgene ingress pipe, when treating that temperature is reduced to 0 ℃, begin to drip 3,4-dichlorphenamide bulk powder solution is after dripping off in 1.6 hours, restir 1.5 hours, be warming up to 135 ℃ with 20 ℃/hour heat-up rates, the restock phosgene stops logical phosgene to material clear state, catch up with phosgene 1h with nitrogen, rectifying gets 68.6 kilograms of pure product, and product purity is 98.7%, with 3,4-dichlorphenamide bulk powder meter, 3,4-dichloro phenylcarbimide total recovery 98.2%, the back light gasification reaction kettle recycles after the solvent treatment.
Embodiment 4:
In the 500L dissolution kettle, add 130 kilograms of orthodichlorobenzenes, add 3,63 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 55 ℃, restir 30 minutes to 1 hour, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 255 kilograms of orthodichlorobenzenes, cooling simultaneously feeds 15 kilograms of phosgene by the phosgene ingress pipe, when treating that temperature is reduced to-5 ℃, begin to drip 3,4-dichlorphenamide bulk powder solution is after dripping off in 1.6 hours, restir 5 hours, be warming up to 150 ℃ with 20 ℃/hour heat-up rates, the restock phosgene stops logical phosgene to material clear state, catch up with phosgene 3h with nitrogen, rectifying gets 71.9 kilograms of pure product, and product purity is 98.6%, with 3,4-dichlorphenamide bulk powder meter, 3,4-dichloro phenylcarbimide total recovery 98%, the back light gasification reaction kettle recycles after the solvent treatment.
Embodiment 5:
In the 500L dissolution kettle, add the dimethylbenzene 120 kg, add 3,52 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 55 ℃, restir 40 minutes to 1 hour, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 250 kilograms of dimethylbenzene, cooling simultaneously feeds 11 kilograms of phosgene by the phosgene ingress pipe, when treating that temperature is reduced to-10 ℃, begin to drip 3,4-dichlorphenamide bulk powder solution is after dripping off in 1.6 hours, restir 1 hour, be warming up to 110 ℃ with 5 ℃/hour heat-up rates, the restock phosgene stops logical phosgene to material clear state, catch up with phosgene 1h with nitrogen, rectifying gets 58.9 kilograms of pure product, and product purity is 98.6%, with 3,4-dichlorphenamide bulk powder meter, 3,4-dichloro phenylcarbimide total recovery 97.2%, the back light gasification reaction kettle recycles after the solvent treatment.
Embodiment 6:
In the 500L dissolution kettle, add the Benzene Chloride 120 kg, add 3,57 kilograms of 4-dichlorphenamide bulk powders start and stir, and open steam valve, slowly are warming up to 60 ℃, and restir 50 minutes is treated solid 3, and the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 240 kilograms of Benzene Chloride, cooling simultaneously feeds 11 kilograms of phosgene by the phosgene ingress pipe, when treating that temperature is reduced to-5 ℃, begin to drip 3,4-dichlorphenamide bulk powder solution is after dripping off in 1.7 hours, restir 2 hours, be warming up to 128 ℃ with 20 ℃/hour heat-up rates, the restock phosgene stops logical phosgene to material clear state, catch up with phosgene 5h with nitrogen, rectifying gets 65 kilograms of pure product, and product purity is 98.5%, with 3,4-dichlorphenamide bulk powder meter, 3,4-dichloro phenylcarbimide total recovery 97.7%, the back light gasification reaction kettle recycles after the solvent treatment.
Embodiment 7:
Method with embodiment 6 is identical, different is in the 500L dissolution kettle, adds the Benzene Chloride 120 kg, adds 3,12 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 60 ℃, restir 50 minutes, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 180 kilograms of Benzene Chloride, cooling simultaneously feeds 3.6 kilograms of phosgene by the phosgene ingress pipe.
Embodiment 8:
Method with embodiment 6 is identical, different is in the 500L dissolution kettle, adds the Benzene Chloride 120 kg, adds 3,66 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 60 ℃, restir 50 minutes, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.In the 500L reactor, add 198 kilograms of Benzene Chloride, cooling simultaneously feeds 9 kilograms of phosgene by the phosgene ingress pipe.
Embodiment 9:
Method with embodiment 6 is identical, different is in the 500L dissolution kettle, adds the Benzene Chloride 120 kg, adds 3,36 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 60 ℃, restir 50 minutes, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.
Embodiment 10:
Method with embodiment 6 is identical, different is in the 500L dissolution kettle, adds the Benzene Chloride 120 kg, adds 3,14.5 kilograms of 4-dichlorphenamide bulk powders, start and stir, open steam valve, slowly be warming up to 60 ℃, restir 50 minutes, treat solid 3, the 4-dichlorphenamide bulk powder is squeezed into elevated dosing vessel with it after dissolving fully.
Claims (6)
1. one kind 3, the preparation method of 4-dichloro phenylcarbimide is characterized in that this method may further comprise the steps:
(1) with 3, the 4-dichlorphenamide bulk powder is dissolved in the organic solvent, and 3, the amount of 4-dichlorphenamide bulk powder is 10～55% of an organic solvent weight;
(2) in reactor, adding weight is 3, the organic solvent that the 4-dichlorphenamide bulk powder is 3～15 times, and feeding weight is 3, the phosgene of 4-dichlorphenamide bulk powder 18～30%;
(3), slowly drip 3 of step (1) preparation, 4-dichlorphenamide bulk powder solution to reactor at-10～0 ℃;
(4) drip after, stirring reaction 1～5 hour, the heat-up rate with 5～20 ℃/h is warming up to 110～150 ℃ again;
When (5) temperature is increased to 110～150 ℃, feed phosgene, be as clear as crystal state until material to reactor;
(6) stop logical phosgene, catch up with phosgene 1～5h with rare gas element;
(7) rectifying obtains 3 after removing solvent, 4-dichloro phenylcarbimide elaboration;
(8) the back light gasification reaction kettle is applied mechanically after the solvent treatment;
Wherein, the organic solvent described in step (1) and the step (2) is toluene, dimethylbenzene, Benzene Chloride, orthodichlorobenzene or santochlor.
2. according to claim 13, the preparation method of 4-dichloro phenylcarbimide is characterized in that the organic solvent in step (1) and the step (2) can be the same or different.
3. according to claim 13, the preparation method of 4-dichloro phenylcarbimide is characterized in that in the step (1), 3, and the amount of 4-dichlorphenamide bulk powder is 12～30% of an organic solvent weight.
4. according to claim 13, the preparation method of 4-dichloro phenylcarbimide is characterized in that in the step (3) that described temperature is-10 ℃～-5 ℃.
5. according to claim 13, the preparation method of 4-dichloro phenylcarbimide is characterized in that in the step (4), temperature is increased to 120～140 ℃.
6. according to claim 13, the preparation method of 4-dichloro phenylcarbimide is characterized in that rare gas element is N described in the step (6)
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810025438XA CN101274904B (en) | 2008-04-28 | 2008-04-28 | Preparation for 3, 4-dichloro phenyl isocyanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810025438XA CN101274904B (en) | 2008-04-28 | 2008-04-28 | Preparation for 3, 4-dichloro phenyl isocyanate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101274904A CN101274904A (en) | 2008-10-01 |
| CN101274904B true CN101274904B (en) | 2011-08-31 |
Family
ID=39994805
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200810025438XA Active CN101274904B (en) | 2008-04-28 | 2008-04-28 | Preparation for 3, 4-dichloro phenyl isocyanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101274904B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739520B (en) * | 2013-12-26 | 2016-03-30 | 安徽广信农化股份有限公司 | A kind of 3,4-dichlorobenzene isocyanic ester process for purification |
| CN108752240A (en) * | 2018-07-13 | 2018-11-06 | 江苏快达农化股份有限公司 | A kind of synthetic method of 1,3- diformazans based isocyanate hexamethylene |
| CN109180530A (en) * | 2018-09-11 | 2019-01-11 | 江西禾益化工股份有限公司 | A kind of method using micro passage reaction preparation 3,5- dichlorophenyl isocyanate |
| CN112358419B (en) * | 2020-11-24 | 2023-04-07 | 浙江丽水有邦新材料有限公司 | Synthesis process of 3, 4-dichlorophenyl isocyanate |
| CN115536552A (en) * | 2022-10-11 | 2022-12-30 | 宁夏瑞泰科技股份有限公司 | Method for synthesizing 1, 5-naphthalene diisocyanate by aqueous phase salifying process |
-
2008
- 2008-04-28 CN CN200810025438XA patent/CN101274904B/en active Active
Non-Patent Citations (3)
| Title |
|---|
| 王绪根.3，4-二氯苯基异氰酸酯连续化生产工艺研发.中国优秀硕士学位论文全文数据库.2005,1-68. * |
| 赵斌等.光气法合成3 4 - 二氯苯基异氰酸酯.河北化工 1.2003 |
| 赵斌等.光气法合成3,4- 二氯苯基异氰酸酯.河北化工 1.2003,(1),25-26. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101274904A (en) | 2008-10-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101274904B (en) | Preparation for 3, 4-dichloro phenyl isocyanate | |
| CA2607099A1 (en) | Production of sodium diformate | |
| EP1530559A1 (en) | Method and device for producing formic acid formates and use of said formates | |
| CN104356028A (en) | Method for continuously preparing 3,4-dichlorophenyl isocyanate | |
| US20150344318A1 (en) | Recyling method of pure ammonium sulfate aqueous solution | |
| CN107337618A (en) | It is a kind of while improve Metformin hydrochloride purity and the production method of yield | |
| CN101962344A (en) | Method for purifying tetrachloroisophthalonitrile crystal | |
| CN110938019B (en) | Continuous synthesis method of isoproturon | |
| EP2425834A1 (en) | Process for the production of l-carnitine tartrate | |
| CN110818603B (en) | Preparation method of methomyl oxime | |
| CN111484426A (en) | Method for synthesizing aminoacetonitrile hydrochloride from hydrocyanic acid | |
| CN113880730B (en) | Industrial method for continuously preparing hexamethylene diisocyanate | |
| CN103360284A (en) | Preparation method of lufenuron compound | |
| CN102558060A (en) | Process for preparing imidazolidine | |
| CN110872242B (en) | Synthesis method of celecoxib intermediate p-hydrazino benzenesulfonamide hydrochloride | |
| AU2019267327B2 (en) | Process for the desulphurization of materials and/or residues containing lead sulphate employing an amino compound | |
| CN107162937A (en) | A kind of synthesis technique of high-quality diuron | |
| CN105001123A (en) | Cold synthesis technology of diuron | |
| EP1154955B1 (en) | Method of producing sodium dicyanamide | |
| CN105017088A (en) | Production process of diuron | |
| CN111054278A (en) | Continuous production process and device for thiodicarb synthesis reaction | |
| CN105037214A (en) | Esterification synthesis technology of diuron | |
| CN113603557B (en) | Process for co-production of dicyandiamide and ammonium nitrate nitrogen fertilizer | |
| CN103130247A (en) | Process for producing ammonium sulfate and hydrogen chloride by employing ammonium chloride and sulfuric acid | |
| CN105481729B (en) | A kind of preparation method of DL- high-cysteic acids |
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 | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 223002 Huaian City, Jiangsu Province Chemical Qingpu District Road No. 30 Patentee after: Andao mai'anbang (Jiangsu) Co., Ltd Address before: 223002 Huaian City, Jiangsu Province Chemical Qingpu District Road No. 30 Patentee before: JIANGSU ANPON ELECTROCHEMICAL Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |