CN111450857A - Catalyst and preparation process of tert-butyl isothiocyanate - Google Patents

Catalyst and preparation process of tert-butyl isothiocyanate Download PDF

Info

Publication number
CN111450857A
CN111450857A CN202010403496.2A CN202010403496A CN111450857A CN 111450857 A CN111450857 A CN 111450857A CN 202010403496 A CN202010403496 A CN 202010403496A CN 111450857 A CN111450857 A CN 111450857A
Authority
CN
China
Prior art keywords
tert
hydrogen chloride
butyl
butyl isothiocyanate
drying container
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
Application number
CN202010403496.2A
Other languages
Chinese (zh)
Other versions
CN111450857B (en
Inventor
任天瑞
陈福勇
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Zaitou Biotechnology Co ltd
Original Assignee
Jiangsu Parrini New Material Technology Co ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Jiangsu Parrini New Material Technology Co ltd filed Critical Jiangsu Parrini New Material Technology Co ltd
Priority to CN202010403496.2A priority Critical patent/CN111450857B/en
Publication of CN111450857A publication Critical patent/CN111450857A/en
Application granted granted Critical
Publication of CN111450857B publication Critical patent/CN111450857B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06Halogens; Compounds thereof
    • B01J27/08Halides
    • B01J27/10Chlorides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16Isothiocyanates
    • C07C331/18Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
    • C07C331/20Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/584Recycling of catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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% tert-butyl alcohol and 200-250 parts of 30% hydrochloric acid according to the mass parts, dissolving the ammonium thiocyanate in the water, adding the 85% tert-butyl alcohol, heating, dropwise adding the 30% hydrochloric acid, standing for layering to obtain an upper layer material, transferring the upper layer material into a drying container, heating to 50-60 ℃, performing vacuumizing operation, introducing dry hydrogen chloride gas into the vacuumizing drying container, closing the valve when the drying container returns to normal pressure, maintaining for 30 +/-5 min, and performing nitrogen replacement to obtain the tert-butyl isothiocyanate. According to the invention, dry hydrogen chloride gas is used as a catalyst for preparing tert-butyl isothiocyanate, the hydrogen chloride is easy to separate, no by-product is generated, the content of prepared tert-butyl isothiocyanate is more than 98%, and the preparation environment of tert-butyl isothiocyanate can be effectively improved.

Description

Catalyst and preparation process of tert-butyl isothiocyanate
Technical Field
The invention relates to a catalyst for preparing tert-butyl isothiocyanate and a preparation process of tert-butyl isothiocyanate, belonging to the technical field of tert-butyl isothiocyanate preparation.
Background
The chemical name of the buprofezin is 2-tert-butylimino-3-isopropyl-5-phenyl-1, 3, 5-thiadiazine-4-ketone, and the molecular formula is C16H23N3OS, which was first developed by pesticide Japan, is a novel selective insecticide for inhibiting the growth and development of insects, has strong contact poisoning effect and stomach poisoning effect, and has the action mechanism of inhibitingThe chitin of the insect is synthesized and interferes with metabolism, so that the nymph is desquamated and malformed or the adult wings are malformed and die slowly. The effect can be shown after 3-7 days after the application of the pesticide, the pesticide has no direct killing power on imagoes, but the service life can be shortened, the egg laying amount is reduced, most of the produced eggs are sterile eggs, and larvae die quickly even when being hatched. The buprofezin has high selectivity, has good control effect on homoptera plant hoppers, leafhoppers, whiteflies and scale insect hydrocarbon pests, and also has durable larvicidal activity on certain coleoptera pests and mites. Can effectively control plant hoppers and leafhoppers on rice, tea, leafhoppers on potatoes, whiteflies on oranges and vegetables, and pelagic and mealybugs on oranges, and can also control scale insects on fruit trees and tea trees, and the like. In China, the buprofezin preparation is sold as "delphacidofol", and is widely used for rice planting.
Buprofezin is synthesized from two intermediates, N-tert-butyl-N-isopropylthiourea and N-chloromethyl-N-phenylcarbamoyl chloride. The N-tert-butyl-N-isopropylthiourea is prepared by using ammonium thiocyanate and tert-butyl alcohol as initial raw materials, synthesizing a mixture of tert-butyl thiocyanate and tert-butyl isothiocyanate, transforming zinc chloride isomeric tert-butyl thiocyanate into tert-butyl isothiocyanate, separating isomeric impurities and zinc chloride at high temperature, distilling and purifying to obtain tert-butyl isothiocyanate with the content of more than 98%, and reacting with isopropylamine to obtain the N-tert-butyl-N-isopropylthiourea. In the process of converting zinc chloride isomeric tert-butyl thiocyanate into tert-butyl isothiocyanate, a high-viscosity substance is generated, and the high-viscosity substance has certain fluidity only at high temperature, so that the production environment is very severe and is difficult to process.
Disclosure of Invention
The invention aims to solve the defects of 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 isomeric tert-butyl thiocyanate into tert-butyl isothiocyanate and influence the production environment in the traditional process.
In order to achieve the above object, the present invention firstly proposes a catalyst for preparing tert-butyl isothiocyanate, which is dry hydrogen chloride gas.
The invention also provides a preparation process of the tert-butyl isothiocyanate, which comprises the following steps:
taking 70-85 parts of ammonium thiocyanate, 200 parts of water, 65-90 parts of 85% tert-butyl alcohol and 200-250 parts of 30% hydrochloric acid according to the mass parts,
adding ammonium thiocyanate into water, stirring to prepare an ammonium thiocyanate solution, adding 85% tert-butyl alcohol into the ammonium thiocyanate solution, heating to 45-50 ℃ to prepare a 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 for layering, and taking an upper-layer material;
transferring the upper material into a drying container, heating to 50-60 ℃, and carrying out hydrogen chloride catalysis operation to obtain the tert-butyl isothiocyanate.
Preferably, in the hydrogen chloride catalysis operation, the drying container is vacuumized, and dried hydrogen chloride gas is introduced into the vacuumized drying container until the drying container returns to the normal pressure and is closed, and nitrogen replacement is performed after the drying container is maintained for 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 catalysis operation, dioxane is used as a solvent to prepare 20% hydrogen chloride dioxane solution, and 4-8 parts of 20% hydrogen chloride dioxane solution is added into a drying container and is maintained for 30 +/-5 min.
Preferably, the stirring is continued for 30min to 90min after the dripping of the 30% hydrochloric acid is finished.
The invention has the following beneficial effects:
the dry hydrogen chloride gas is used as a catalyst for preparing the tert-butyl isothiocyanate, the hydrogen chloride is easy to separate, no by-product is generated, the prepared 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 technical solutions of the present invention are described in detail below to make them easier to understand and master.
Firstly, the scheme provides a catalyst for preparing tert-butyl isothiocyanate, and the catalyst is dry hydrogen chloride gas. The dry hydrogen chloride gas belongs to the prior art, and more particularly, the water mass fraction in the hydrogen chloride gas<1.0×10-4
The preparation process of tert-butyl isothiocyanate is explained in detail as follows:
taking 70-85 parts of ammonium thiocyanate, 200 parts of water, 65-90 parts of 85% tert-butyl alcohol and 200-250 parts of 30% hydrochloric acid according to the mass parts.
Adding ammonium thiocyanate into water, stirring to prepare an ammonium thiocyanate solution, adding 85% tert-butyl alcohol into the ammonium thiocyanate solution, heating to 45-50 ℃ to prepare a 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 finished. Stopping stirring, standing and layering, and taking the upper layer material.
Transferring the upper-layer material into a drying container, heating the volume of the drying container to 50-60 ℃ until the volume of the drying container is 1-1.5 times of the volume of water, vacuumizing the drying container to 0.08-0.09 MPa, introducing dry hydrogen chloride gas into the vacuumizing drying container, closing the drying container at normal pressure, maintaining the pressure for 30 +/-5 min, and performing nitrogen replacement to obtain the tert-butyl isothiocyanate.
Example one
Adding 76.1 g of ammonium thiocyanate into 200g of water, stirring to dissolve, adding 87 g of 85% tert-butyl alcohol, heating to 45 ℃, adding 220g of 30% hydrochloric acid within 30 minutes, keeping the reflux state for 2 hours, stopping stirring, standing, removing lower-layer water, obtaining 96 g of upper-layer materials, and detecting that the content of tert-butyl thiocyanate is 54% and the content of tert-butyl isothiocyanate is 46%.
Transferring the material to a dry 250 ml flask, heating to 50 ℃, vacuumizing the flask to 0.09MPa, connecting a glass tube inserted with the material to a hydrogen chloride steel bottle, and opening a valve to restore the pressure in the flask to normal pressure. After 30 minutes of holding, nitrogen was purged. Sampling and detecting the content of the tert-butyl isothiocyanate to be 98.3 percent.
Example two
Adding 95 g of ammonium thiocyanate into 250g of water, stirring to dissolve the ammonium thiocyanate, adding 87 g of 85% tert-butyl alcohol, heating to 45-50 ℃, adding 250g of 30% hydrochloric acid within 30 minutes, keeping the reflux state for 1.5 hours, stopping stirring, standing, removing lower-layer water, obtaining 105 g of upper-layer materials, and detecting that the content of tert-butyl thiocyanate is 51% and the content of tert-butyl isothiocyanate is 48%.
Transferring the material to a dry 250 ml flask, heating to 55 ℃, vacuumizing the flask to 0.08MPa, connecting a glass tube inserted with the material to a hydrogen chloride steel bottle, and opening a valve to restore the pressure in the flask to normal pressure. After holding for 25 minutes, nitrogen was purged. Sampling and detecting the content of the tert-butyl isothiocyanate to be 98.5 percent.
EXAMPLE III
76.1 g of ammonium thiocyanate is added into 200g of water, 87 g of 85% tert-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 layer of water is removed by standing, 97 g of upper layer material is obtained, the content of tert-butyl thiocyanate is detected to be 38%, and the content of tert-butyl isothiocyanate is 62%.
Transferring the material to a dry 250 ml flask, heating to 60 ℃, vacuumizing the flask to 0.09MPa, connecting a glass tube inserted with the material to a hydrogen chloride steel bottle, and opening a valve to restore the pressure in the flask to normal pressure. After 30 minutes of holding, nitrogen was purged. Sampling and detecting the content of the tert-butyl isothiocyanate to be 98.7 percent.
Example four
82.2 g of ammonium thiocyanate is added into 200g of water, 78 g of 85% tert-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 layer water is removed by standing, the upper layer material is 94 g, the content of tert-butyl thiocyanate is detected to be 58%, and the content of tert-butyl isothiocyanate is 42%.
Transferring the material to a dry 250 ml flask, heating to 55 ℃, vacuumizing the flask to 0.09MPa, inserting a glass tube into the material into a hydrogen chloride steel bottle, and opening a valve to restore the pressure in the flask to normal pressure. After 30 minutes of holding, nitrogen was purged. Sampling and detecting the content of the tert-butyl isothiocyanate to be 98.6 percent.
EXAMPLE five
Adding 76.1 g of ammonium thiocyanate into 200g of water, stirring to dissolve, adding 87 g of 85% tert-butyl alcohol, heating to 45 ℃, adding 220g of 30% hydrochloric acid within 30 minutes, keeping the reflux state for 2 hours, stopping stirring, standing, removing lower-layer water, obtaining 96 g of upper-layer materials, and detecting that the content of tert-butyl thiocyanate is 54% and the content of tert-butyl isothiocyanate is 46%.
The material was transferred to a dry 250 ml flask, heated to 55 ℃ and dried hydrogen chloride was dissolved in dioxane solvent to prepare a 20% hydrogen chloride dioxane solution, 5g of 20% hydrogen chloride dioxane solution was added to the flask, which was kept for 30 minutes and the content of t-butyl isothiocyanate was checked to be 98.8%.
The catalyst for preparing the tert-butyl isothiocyanate and the preparation process of the tert-butyl isothiocyanate disclosed by the invention can be found through the above description, dry hydrogen chloride gas is used as the catalyst for preparing the tert-butyl isothiocyanate, the hydrogen chloride is easy to separate, no by-product is generated, the content of the prepared tert-butyl isothiocyanate is more than 98%, and meanwhile, the preparation environment of the tert-butyl isothiocyanate can be effectively improved.
The technical solutions of the present invention are fully described above, it should be noted that the specific embodiments of the present invention are not limited by the above description, and all technical solutions formed by equivalent or equivalent changes in structure, method, or function according to the spirit of the present invention by those skilled in the art are within the scope of the present invention.

Claims (6)

1. A catalyst for the preparation of tert-butyl isothiocyanate characterized by:
the catalyst is dry hydrogen chloride gas.
2. The preparation process of tert-butyl isothiocyanate is characterized by comprising the following steps:
taking 70-85 parts of ammonium thiocyanate, 200 parts of water, 65-90 parts of 85% tert-butyl alcohol and 200-250 parts of 30% hydrochloric acid according to the mass parts,
adding ammonium thiocyanate into water, stirring to prepare an ammonium thiocyanate solution, adding 85% tert-butyl alcohol into the ammonium thiocyanate solution, heating to 45-50 ℃ to prepare a 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 for layering, and taking an upper-layer material;
transferring the upper material into a drying container, heating to 50-60 ℃, and carrying out hydrogen chloride catalysis operation to obtain the tert-butyl isothiocyanate.
3. The process for preparing tert-butyl isothiocyanate according to claim 2, wherein:
in the hydrogen chloride catalysis operation, the drying container is vacuumized, and dry hydrogen chloride gas is introduced into the vacuumized drying container until the drying container returns to a normal pressure and is closed, and nitrogen replacement is carried out after the drying container is maintained for 30 +/-5 min.
4. The process for preparing tert-butyl isothiocyanate according to claim 3, wherein:
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.
5. The process for preparing tert-butyl isothiocyanate according to claim 2, wherein:
in the hydrogen chloride catalysis operation, dioxane is used as a solvent to prepare 20% hydrogen chloride dioxane solution, and 4-8 parts of 20% hydrogen chloride dioxane solution is added into a drying container and is maintained for 30 +/-5 min.
6. The process for preparing tert-butyl isothiocyanate according to claim 2, wherein:
and continuously stirring for 30-90 min after the dripping of the 30% hydrochloric acid is finished.
CN202010403496.2A 2020-05-13 2020-05-13 Catalyst and preparation process of tert-butyl isothiocyanate Active CN111450857B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010403496.2A CN111450857B (en) 2020-05-13 2020-05-13 Catalyst and preparation process of tert-butyl isothiocyanate

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010403496.2A CN111450857B (en) 2020-05-13 2020-05-13 Catalyst and preparation process of tert-butyl isothiocyanate

Publications (2)

Publication Number Publication Date
CN111450857A true CN111450857A (en) 2020-07-28
CN111450857B CN111450857B (en) 2023-06-13

Family

ID=71672341

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010403496.2A Active CN111450857B (en) 2020-05-13 2020-05-13 Catalyst and preparation process of tert-butyl isothiocyanate

Country Status (1)

Country Link
CN (1) CN111450857B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1092785A (en) * 1992-12-04 1994-09-28 希巴-盖吉股份公司 Oligomeric HALS phosphorous acid ester and HALS phosphinate with used as stabilizers
CN1124734A (en) * 1994-12-14 1996-06-19 日本烟业产业株式会社 Thiazine- or thiazepine-derivatives
CA2207953A1 (en) * 1996-06-28 1997-12-28 Randall Wayne Stephens Process for the manufacture of acetonylbenzamides
CN101245160A (en) * 2008-03-11 2008-08-20 四川大学 Fire retardant thermoplastic resin composition and manufacture method thereof
JP2011195584A (en) * 2010-02-26 2011-10-06 Mitsui Chemicals Inc Transition metal complex compound, olefin polymerizing catalyst containing the compound, and method for producing olefin polymer which is carried out in the presence of the catalyst
CN102241573A (en) * 2010-05-10 2011-11-16 陕西唐正科技发展有限公司 Preparation method of 3,3-methyl butyraldehyde
WO2014017447A1 (en) * 2012-07-25 2014-01-30 昭和電工株式会社 Membrane electrode assembly and fuel cell provided with same
CN103755612A (en) * 2013-12-20 2014-04-30 浙江普康化工有限公司 Method for synthesizing phenyl isothiocyanate
CN103936690A (en) * 2005-10-25 2014-07-23 盐野义制药株式会社 Aminodihydrothiazine Derivative
CN104177473A (en) * 2014-08-20 2014-12-03 山东奔月生物科技有限公司 Synthesis method of neotame
CN110446696A (en) * 2017-03-24 2019-11-12 三井化学株式会社 The manufacturing method of multi-thiol compound, polymerizable composition, polymerizable composition and application thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1092785A (en) * 1992-12-04 1994-09-28 希巴-盖吉股份公司 Oligomeric HALS phosphorous acid ester and HALS phosphinate with used as stabilizers
CN1124734A (en) * 1994-12-14 1996-06-19 日本烟业产业株式会社 Thiazine- or thiazepine-derivatives
CA2207953A1 (en) * 1996-06-28 1997-12-28 Randall Wayne Stephens Process for the manufacture of acetonylbenzamides
CN103936690A (en) * 2005-10-25 2014-07-23 盐野义制药株式会社 Aminodihydrothiazine Derivative
CN101245160A (en) * 2008-03-11 2008-08-20 四川大学 Fire retardant thermoplastic resin composition and manufacture method thereof
JP2011195584A (en) * 2010-02-26 2011-10-06 Mitsui Chemicals Inc Transition metal complex compound, olefin polymerizing catalyst containing the compound, and method for producing olefin polymer which is carried out in the presence of the catalyst
CN102241573A (en) * 2010-05-10 2011-11-16 陕西唐正科技发展有限公司 Preparation method of 3,3-methyl butyraldehyde
WO2014017447A1 (en) * 2012-07-25 2014-01-30 昭和電工株式会社 Membrane electrode assembly and fuel cell provided with same
CN103755612A (en) * 2013-12-20 2014-04-30 浙江普康化工有限公司 Method for synthesizing phenyl isothiocyanate
CN104177473A (en) * 2014-08-20 2014-12-03 山东奔月生物科技有限公司 Synthesis method of neotame
CN110446696A (en) * 2017-03-24 2019-11-12 三井化学株式会社 The manufacturing method of multi-thiol compound, polymerizable composition, polymerizable composition and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
孙致远等: "噻嗪酮的合成", 《农药》 *
黄金艳;: "2-氯-5-氯甲基-1,3-噻唑的合成" *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Also Published As

Publication number Publication date
CN111450857B (en) 2023-06-13

Similar Documents

Publication Publication Date Title
WO2022127943A1 (en) Low-spore variety of ganoderma lucidum having high polysaccharide yield and artificial cultivation method therefor
CN111450857A (en) Catalyst and preparation process of tert-butyl isothiocyanate
CN107517995B (en) Formula for improving storage capacity of hybrid rice seeds, preparation method and application
CN102217591A (en) Environmentally-friendly abamectin ointment production process
KR20150067305A (en) Yield enhancement for stress-susceptible plants
CN104803879A (en) Preparation technology of methoxyfenozide
CN1687420A (en) Gene hrpNECCS of multifunctional activity of coded plant and signal factor of broad-spectrum resistance cell, and expression production Harpin ECCS
CN109705048B (en) Clean preparation method of tebuconazole
CN108250156B (en) Cinnamylate oxadiazine derivative and preparation method and application thereof
CN105503680B (en) The method for improving Cupric sulfate centrifuge mother liquor flour extraction
Ying-qian et al. Advances in Actinidia research in China
CN110178845B (en) Growth-promoting disease-resistant organic rare earth compound and preparation method and application thereof
CN112244024A (en) Process for producing mepiquat chloride aqueous solution by continuous method
TW201805275A (en) Processes for preparing 5-(chloromethyl)furfural
CN110613750B (en) Preparation method of soluble cinnamomum longepaniculatum essential oil powder
CN106244184B (en) A kind of method that pyrolysis gas of biomass catalytic pyrolysis prepares BTX
Lee et al. Effect of watering control on growth and bulb size of plug seedling in onion (Allium cepa L.) set production
CN108419607A (en) A kind of process parameter optimizing method of oyster cap fungus degradation cotton stalk
CN109369573B (en) Preparation method of sex pheromone intermediate of fall webworm
CN216192256U (en) Rice bacterial leaf blight suspension liquid preparation box
CN114438011B (en) Fermentation production method and application of beauveria bassiana PfBb spore powder
CN114920792B (en) Steroid compound and preparation method and application thereof
CN105622541A (en) Synthesis method of 3-methyl-4-nitroiminoperhydro-1,3,5-oxadiazine
CN109315404B (en) Application of 11-dehydrokalaineanone in antifeedant activity and inhibition of growth and development of insects
CN114702422A (en) Preparation method of diafenthiuron technical

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
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20230620

Address after: 215314 No. 508, Huangpujiang North Road, Zhoushi Town, Kunshan City, Suzhou City, Jiangsu Province

Patentee after: Jiangsu zaitou Biotechnology Co.,Ltd.

Address before: Room 306, Building 3, Dongchuang Technology Center, Qianjin East Road Enterprise Science Park, Kunshan Development Zone, Suzhou City, Jiangsu Province, 215300

Patentee before: Jiangsu parrini New Material Technology Co.,Ltd.