CN111450857B - Catalyst and preparation process of tert-butyl isothiocyanate - Google Patents
Catalyst and preparation process of tert-butyl isothiocyanate Download PDFInfo
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- CN111450857B CN111450857B CN202010403496.2A CN202010403496A CN111450857B CN 111450857 B CN111450857 B CN 111450857B CN 202010403496 A CN202010403496 A CN 202010403496A CN 111450857 B CN111450857 B CN 111450857B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
- C07C331/16—Isothiocyanates
- C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
- C07C331/20—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
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Abstract
The invention discloses a catalyst and a preparation process of tert-butyl isothiocyanate, wherein the catalyst is dry hydrogen chloride gas. Taking 70-85 parts of ammonium thiocyanate, 200 parts of water, 65-90 parts of 85% tertiary butanol and 200-250 parts of 30% hydrochloric acid according to parts by weight, dissolving ammonium thiocyanate in water, adding 85% tertiary butanol, heating, dripping 30% hydrochloric acid, standing for layering, taking an upper material, transferring the upper material into a drying container, heating to 50-60 ℃, vacuumizing, introducing dry hydrogen chloride gas into the vacuumizing drying container, recovering normal pressure to the drying container, closing a valve, maintaining for 30+/-5 min, and then performing nitrogen replacement to obtain tert-butyl isothiocyanate. According to the invention, the dried hydrogen chloride gas is used as the catalyst for preparing the tert-butyl isothiocyanate, the hydrogen chloride is easy to separate, no byproduct is generated, the preparation of the tert-butyl isothiocyanate reaches more than 98%, and meanwhile, the preparation environment of the tert-butyl isothiocyanate can be effectively improved.
Description
Technical Field
The invention relates to a catalyst for preparing tert-butyl isothiocyanate and a preparation process of tert-butyl isothiocyanate, and belongs to the technical field of preparation of tert-butyl isothiocyanate.
Background
The buprofezin has the chemical name of 2-tert-butylimino-3-isopropyl-5-phenyl-1, 3, 5-thiadiazine-4-ketone and the molecular formula of C 16 H 23 N 3 OS, which was developed by japanese pesticide company for the first time, is a novel selective pesticide for inhibiting the growth and development of insects, has a strong contact killing effect and also has a stomach poisoning effect, and has a mechanism of action of inhibiting chitin synthesis and interfering metabolism of insects, so that nymphs are malformed or adult wings are malformed after desquamation and die slowly. The Chinese medicinal composition can be used for treating the adult with the advantages of obvious effect after being applied for 3-7 days, no direct killing power to the adult, shortened service life, reduced spawning quantity, and produced sterile eggs, and the larvae die quickly even if hatching. The buprofezin has high selectivity, has good control effect on plant hoppers, leafhoppers, whiteflies and hydrocarbon pests of homoptera, and also has lasting larvicide activity on certain coleoptera pests and mites. Can effectively prevent and treat plant hoppers and leafhoppers on rice, tea, leafhoppers on potatoes, oranges and white flies on vegetables, scale insects on oranges and white flies, scale insects on fruit trees and tea trees, and the like. In China, the method has the advantages that,the buprofezin preparation is a commodity name of prometryn and is widely used for paddy rice planting.
Buprofezin is synthesized from two intermediates, N-tert-butyl-N-isopropylthiourea and N-chloromethyl-N-phenylcarbamoyl chloride. The N-tertiary butyl-N-isopropylthiourea is prepared by taking ammonium thiocyanate and tertiary butyl alcohol as initial raw materials, firstly synthesizing a mixture of tertiary butyl thiocyanate and tertiary butyl isothiocyanate, then converting zinc chloride isomerism tertiary butyl thiocyanate into tertiary butyl isothiocyanate, separating isomerism impurities and zinc chloride at high temperature, distilling and purifying to obtain the tertiary butyl isothiocyanate with the content of more than 98%, and then reacting with isopropylamine to obtain the N-tertiary butyl-N-isopropylthiourea. In the process of converting zinc chloride isomerism tert-butyl thiocyanate into tert-butyl isothiocyanate, a high-viscosity substance is generated, and the zinc chloride isomerism tert-butyl thiocyanate has certain fluidity only at high temperature, so that the production environment is very bad and is difficult to process.
Disclosure of Invention
The invention aims to solve the defects in the prior art, and provides a catalyst for preparing tert-butyl isothiocyanate and a preparation process of tert-butyl isothiocyanate, aiming at the problem that high-viscosity substances are generated in the process of converting zinc chloride isomerism tert-butyl thiocyanate into tert-butyl isothiocyanate in the traditional process and influence on production environment.
In order to achieve the above object, the present invention first proposes a catalyst for preparing t-butyl isothiocyanate, which is a dry hydrogen chloride gas.
The invention also provides a preparation process of the tert-butyl isothiocyanate, which comprises the following steps:
according to the mass portions, 70 to 85 portions of ammonium thiocyanate, 200 portions of water, 65 to 90 portions of 85 percent tertiary butanol and 200 to 250 portions of 30 percent hydrochloric acid are taken,
adding ammonium thiocyanate into water, stirring to obtain ammonium thiocyanate solution, adding 85% tertiary butanol into the ammonium thiocyanate solution, heating to 45-50 ℃ to obtain mixed solution, dropwise adding 30% hydrochloric acid into the mixed solution for 30+ -5 min, continuously stirring in the dropwise adding process, stopping stirring, standing and layering, and taking an upper material;
transferring the upper material into a drying container, heating to 50-60 ℃, and then carrying out hydrogen chloride catalytic operation to obtain the tert-butyl isothiocyanate.
Preferably, in the hydrogen chloride catalytic operation, the drying container is vacuumized, and the vacuumized drying container is connected with the dried hydrogen chloride gas, the valve is closed until the drying container is restored to normal pressure, and nitrogen replacement is carried out after 30+/-5 min.
Preferably, the volume of the drying container is 1-1.5 times of the volume of water, and the drying container is vacuumized to 0.08-0.09 MPa.
Preferably, in the hydrogen chloride catalytic operation, a 20% hydrogen chloride dioxane solution is prepared by using dioxane as a solvent, and 4-8 parts of the 20% hydrogen chloride dioxane solution is added into a drying container for 30+/-5 min.
Preferably, stirring is continued for 30-90 min after the completion of the dropwise addition of 30% hydrochloric acid.
The beneficial effects of the invention are mainly as follows:
the dry hydrogen chloride gas is used as the catalyst for preparing the tert-butyl isothiocyanate, the hydrogen chloride is easy to separate and has no byproduct generation, the preparation of the tert-butyl isothiocyanate reaches more than 98 percent, and the preparation environment of the tert-butyl isothiocyanate can be effectively improved.
Detailed Description
The invention provides a catalyst for preparing tert-butyl isothiocyanate and a preparation process of tert-butyl isothiocyanate. The following detailed description of the present invention is provided to facilitate understanding and grasping thereof.
First, a catalyst for preparing tert-butyl isothiocyanate is proposed, which is a dry hydrogen chloride gas. The dry hydrogen chloride gas belongs to the prior art, and more finely, the mass fraction of water in the hydrogen chloride gas<1.0×10 -4 。
The preparation process of the tert-butyl isothiocyanate is described in detail:
according to the mass portion, 70 to 85 portions of ammonium thiocyanate, 200 portions of water, 65 to 90 portions of 85 percent tertiary butanol and 200 to 250 portions of 30 percent hydrochloric acid are taken.
Adding ammonium thiocyanate into water, stirring to obtain ammonium thiocyanate solution, adding 85% tertiary butanol into the ammonium thiocyanate solution, heating to 45-50 ℃ to obtain mixed solution, dropwise adding 30% hydrochloric acid into the mixed solution for 30+ -5 min, continuously stirring in the dropwise adding process, and continuously stirring for 30-90 min after the dropwise adding of 30% hydrochloric acid is completed. Stopping stirring, standing and layering, and taking the upper material.
Transferring the upper material into a drying container, wherein the volume of the drying container is 1-1.5 times of the volume of water, heating to 50-60 ℃, vacuumizing to 0.08-0.09 MPa, introducing dry hydrogen chloride gas into the vacuumizing drying container, recovering normal pressure to the drying container, closing a valve, maintaining for 30+/-5 min, and then performing nitrogen replacement to obtain tert-butyl isothiocyanate.
Example 1
76.1 g of ammonium thiocyanate is added into 200g of water, 87 g of 85% tertiary butyl alcohol is added after stirring and dissolving, the temperature is raised to 45 ℃, 220g of 30% hydrochloric acid is added within 30 minutes, the reflux state is kept for 2 hours, stirring is stopped, the lower water layer is separated still, 96 g of upper material is obtained, and the content of the tertiary butyl thiocyanate is detected to be 54%, and the content of the tertiary butyl isothiocyanate is detected to be 46%.
The materials are transferred into a dry 250 ml flask, the temperature is raised to 50 ℃, the flask is vacuumized to 0.09MPa, a glass tube inserted with the materials is connected into a hydrogen chloride steel bottle, and a valve is opened to restore the pressure in the flask to normal pressure. After 30 minutes of hold, nitrogen was purged. The sample was taken to detect 98.3% t-butyl isothiocyanate.
Example two
95 g of ammonium thiocyanate is added into 250g of water, 87 g of 85% tertiary butyl alcohol is added after stirring and dissolving, the temperature is raised to 45-50 ℃, 250g of 30% hydrochloric acid is added within 30 minutes, the reflux state is kept for 1.5 hours, stirring is stopped, the lower water layer is separated at rest, 105 g of upper material is obtained, and the content of the tertiary butyl thiocyanate is detected to be 51%, and the content of the tertiary butyl isothiocyanate is detected to be 48%.
The materials are transferred into a dry 250 ml flask, the temperature is raised to 55 ℃, the flask is vacuumized to 0.08MPa, a glass tube inserted with the materials is connected into a hydrogen chloride steel bottle, and a valve is opened to restore the pressure in the flask to normal pressure. After 25 minutes of hold, nitrogen was purged. The sample was taken to detect 98.5% t-butyl isothiocyanate.
Example III
76.1 g of ammonium thiocyanate is added into 200g of water, 87 g of 85% tertiary butyl alcohol is added after stirring and dissolving, the temperature is raised to 50 ℃, 250g of 30% hydrochloric acid is added within 30 minutes, the reflux state is kept for half an hour, stirring is stopped, the lower water layer is removed at rest, 97 g of upper material is obtained, and the content of tertiary butyl thiocyanate is detected to be 38%, and the content of tertiary butyl isothiocyanate is detected to be 62%.
The materials are transferred into a dry 250 ml flask, the temperature is raised to 60 ℃, the flask is vacuumized to 0.09MPa, a glass tube inserted with the materials is connected into a hydrogen chloride steel bottle, and a valve is opened to restore the pressure in the flask to normal pressure. After 30 minutes of hold, nitrogen was purged. The sample was taken to detect 98.7% t-butyl isothiocyanate.
Example IV
82.2 g of ammonium thiocyanate is added into 200g of water, 78 g of 85% tertiary butyl alcohol is added after stirring and dissolving, the temperature is raised to 45 ℃, 200g of 30% hydrochloric acid is added within 30 minutes, the reflux state is kept for 1.5 hours, stirring is stopped, the lower water layer is separated still, 94 g of upper material is obtained, and the content of tertiary butyl thiocyanate is detected to be 58%, and the content of tertiary butyl isothiocyanate is detected to be 42%.
Transferring the materials into a dry 250 ml flask, heating to 55 ℃, vacuumizing the flask to 0.09MPa, inserting a glass tube of the materials into a hydrogen chloride steel bottle, opening a valve, and recovering the pressure in the flask to normal pressure. After 30 minutes of hold, nitrogen was purged. The sample was taken to detect 98.6% t-butyl isothiocyanate.
Example five
76.1 g of ammonium thiocyanate is added into 200g of water, 87 g of 85% tertiary butyl alcohol is added after stirring and dissolving, the temperature is raised to 45 ℃, 220g of 30% hydrochloric acid is added within 30 minutes, the reflux state is kept for 2 hours, stirring is stopped, the lower water layer is separated still, 96 g of upper material is obtained, and the content of the tertiary butyl thiocyanate is detected to be 54%, and the content of the tertiary butyl isothiocyanate is detected to be 46%.
The material was transferred to a dry 250 ml flask, heated to 55℃and dried hydrogen chloride was dissolved in dioxane solvent to give a 20% hydrogen chloride dioxane solution, 5g of 20% hydrogen chloride dioxane solution was added to the flask, and the flask was kept for 30 minutes to detect the t-butyl isothiocyanate content of 98.8%.
As can be seen from the above description, the catalyst for preparing tert-butyl isothiocyanate and the preparation process of tert-butyl isothiocyanate of the present invention adopt dry hydrogen chloride gas as the catalyst for preparing tert-butyl isothiocyanate, the hydrogen chloride is easy to separate and no by-product is generated, the preparation of tert-butyl isothiocyanate reaches more than 98%, and the preparation environment of tert-butyl isothiocyanate can be effectively improved.
While the foregoing has been described in terms of embodiments of the present invention, it will be appreciated that the embodiments of the invention are not limited by the foregoing description, but rather, all embodiments of the invention may be modified in structure, method or function by one skilled in the art to incorporate the teachings of this invention, as expressed in terms of equivalent or equivalent embodiments, without departing from the scope of the invention.
Claims (3)
1. The preparation process of the tert-butyl isothiocyanate is characterized by comprising the following steps:
according to the mass portions, 70 to 85 portions of ammonium thiocyanate, 200 portions of water, 65 to 90 portions of 85 percent tertiary butanol and 200 to 250 portions of 30 percent hydrochloric acid are taken,
adding ammonium thiocyanate into water, stirring to obtain ammonium thiocyanate solution, adding 85% tertiary butanol into the ammonium thiocyanate solution, heating to 45-50 ℃ to obtain mixed solution, dropwise adding 30% hydrochloric acid into the mixed solution for 30+ -5 min, continuously stirring in the dropwise adding process, stopping stirring, standing and layering, and taking an upper material;
transferring the upper material into a drying container, heating to 50-60 ℃, and then carrying out dry hydrogen chloride catalytic operation to obtain tert-butyl isothiocyanate, wherein the mass fraction of water in the hydrogen chloride gas<1.0×10 -4 ;
In the hydrogen chloride catalytic operation, the drying container is vacuumized, and the vacuumized drying container is connected with dry hydrogen chloride gas until the drying container is recovered to normal pressure, the valve is closed, and nitrogen replacement is carried out after 30+/-5 min.
2. The process for preparing tert-butyl isothiocyanate according to claim 1, wherein:
the volume of the drying container is 1 to 1.5 times of the volume of water, and the drying container is vacuumized to 0.08 to 0.09MPa.
3. The process for preparing tert-butyl isothiocyanate according to claim 1, wherein:
and continuously stirring for 30-90 min after the dropwise adding of 30% hydrochloric acid is completed.
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CN112774606A (en) * | 2020-12-24 | 2021-05-11 | 安道麦安邦(江苏)有限公司 | Production method and equipment of high-purity buprofezin intermediate 1-isopropyl-3-tert-butylthiourea |
CN113751205A (en) * | 2021-09-10 | 2021-12-07 | 紫金矿业集团股份有限公司 | N-tert-butyl ester collecting agent and preparation method thereof |
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