CN107602476B - Preparation method of 2-mercapto-1-methylimidazole - Google Patents
Preparation method of 2-mercapto-1-methylimidazole Download PDFInfo
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- CN107602476B CN107602476B CN201710939304.8A CN201710939304A CN107602476B CN 107602476 B CN107602476 B CN 107602476B CN 201710939304 A CN201710939304 A CN 201710939304A CN 107602476 B CN107602476 B CN 107602476B
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- methylimidazole
- tert
- mercapto
- dimethyl acetal
- boron trifluoride
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- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims abstract description 14
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 14
- HUMIEJNVCICTPJ-UHFFFAOYSA-N 2,2-dimethoxy-n-methylethanamine Chemical compound CNCC(OC)OC HUMIEJNVCICTPJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- MYFBFSXUSNQNBO-UHFFFAOYSA-N 2-tert-butylsulfanyl-1-methylimidazole Chemical compound CN1C=CN=C1SC(C)(C)C MYFBFSXUSNQNBO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- CCGAYDPMIVSQPK-UHFFFAOYSA-N 2-methyl-2-nitrososulfanylpropane Chemical compound CC(C)(C)SN=O CCGAYDPMIVSQPK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 9
- CRZJPEIBPQWDGJ-UHFFFAOYSA-N 2-chloro-1,1-dimethoxyethane Chemical compound COC(CCl)OC CRZJPEIBPQWDGJ-UHFFFAOYSA-N 0.000 claims description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- LFETXMWECUPHJA-UHFFFAOYSA-N methanamine;hydrate Chemical compound O.NC LFETXMWECUPHJA-UHFFFAOYSA-N 0.000 claims description 5
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical group FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical group Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- MEMUCXUKCBNISQ-UHFFFAOYSA-N acetonitrile;trifluoroborane Chemical compound CC#N.FB(F)F MEMUCXUKCBNISQ-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 claims description 3
- -1 tert-butyl sulfur nitrile Chemical class 0.000 claims description 3
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 13
- 239000002994 raw material Substances 0.000 abstract description 12
- 238000001816 cooling Methods 0.000 abstract description 8
- 239000000126 substance Substances 0.000 abstract description 6
- PDUDJCMHIBRVGF-UHFFFAOYSA-N 1,1,1-trichloro-2,2-dimethoxyethane Chemical compound COC(OC)C(Cl)(Cl)Cl PDUDJCMHIBRVGF-UHFFFAOYSA-N 0.000 abstract 1
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 230000006837 decompression Effects 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 229960002178 thiamazole Drugs 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 238000005915 ammonolysis reaction Methods 0.000 description 1
- 239000003200 antithyroid agent Substances 0.000 description 1
- 229940043671 antithyroid preparations Drugs 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method of electronic grade 2-mercapto-1-methylimidazole, which comprises the following steps: 1) performing a tank-closing reaction on chloral dimethyl acetal and methylamine aqueous solution at the temperature of 80-85 ℃ for 16 hours, cooling, releasing pressure, extracting by using a solvent, concentrating the solvent, and performing reduced pressure rectification to obtain an intermediate methylamino acetaldehyde dimethyl acetal; 2) reacting methylamino acetaldehyde dimethyl acetal and tert-butyl thionitrile under the catalysis of boron trifluoride at 50-70 ℃ to perform condensation reaction to obtain 2-tert-butylthio-1-methylimidazole; 3) adding a solvent into 2-tert-butylthio-1-methylimidazole, adding a catalyst and an organic solvent, reacting at normal temperature, filtering, concentrating filtrate, and crystallizing by using electronic grade water to obtain the product 2-mercapto-1-methylimidazole. The raw materials adopted by the invention are low in price and environment-friendly, the synthetic method is simple and convenient to operate, and the product quality meets the application standard of electronic chemicals.
Description
The technical field is as follows:
the invention belongs to the field of organic chemistry, and particularly relates to a preparation method of 2-mercapto-1-methylimidazole.
Background art:
2-mercapto-1-methylimidazole is an antithyroid agent and is commonly used in medicine. In recent years, the liquid crystal material has been found to play an important role in liquid crystal materials, and is attracted attention and researched by a great number of electronic chemical manufacturers.
At present, the literature reports methods for synthesizing 2-mercapto-1-methylimidazole, which mainly include two methods:
1) first Synthesis method
The method comprises the steps of taking bromoacetaldehyde dimethyl acetal and methylamine water solution as raw materials, carrying out ammonolysis reaction to obtain an intermediate methylamino acetaldehyde dimethyl acetal, and then reacting with potassium thiocyanate to obtain a target product
The synthetic route is as follows:
however, the synthesis method has the defects of high cost of the bromoacetaldehyde dimethyl acetal and the like.
2) Second Synthesis method
Guziec et al (J.Org.chem.1994, 59, 4691-4692) in the prior art disclose a preparation method of methimazole, which takes N-methylimidazole as a raw material to react with N-butyl lithium, and then sulfur powder is added for reflux reaction, and finally the yield of the crude methimazole is 42%.
The synthetic route is as follows:
the method has harsh reaction conditions, and the dropwise addition of the n-butyl lithium is carried out at-78 ℃, so that the industrial scale-up production is difficult.
The invention content is as follows:
in order to overcome the defects, the invention aims to provide the preparation method of the 2-mercapto-1-methylimidazole, which has the advantages of simple process and mild conditions and is completely suitable for industrial production.
The preparation method of the 2-mercapto-1-methylimidazole is technically characterized by comprising the following steps of:
step one, performing tank closing reaction on chloroacetaldehyde dimethyl acetal and methylamine water solution at the temperature of 80-85 ℃, and performing reduced pressure rectification to obtain methylamino acetaldehyde dimethyl acetal;
secondly, methylamino acetaldehyde dimethyl acetal and tert-butyl thionitrile react under the catalysis of boron trifluoride at 50-70 ℃ to perform condensation reaction to obtain 2-tert-butylthio-1-methylimidazole;
adding a solvent into 2-tert-butylthio-1-methylimidazole, adding a catalyst and an organic solvent, reacting at normal temperature, filtering, concentrating the filtrate, and recrystallizing with water to obtain 2-mercapto-1-methylimidazole;
the reaction route is as follows:
further, in the first step, a 50-65% concentration of methylamine water solution is adopted.
Further, in the first step, the ratio of chloroacetaldehyde dimethyl acetal to methylamine is 1: 2.5-3.5.
Further, in the second step, boron trifluoride is boron trifluoride-diethyl ether, boron trifluoride-tetrahydrofuran or boron trifluoride-acetonitrile.
Further, in the second step, the molar ratio of methylamino acetaldehyde dimethyl acetal, tert-butyl sulfur nitrile and boron trifluoride is 1: 0.95-1.05: 0.05-0.15.
Further, in the third step, the organic solvent is toluene, xylene or anisole.
Further, in the third step, the catalyst is selected from aluminum trichloride or boron trichloride, and the adding amount is 0.10-0.15 equivalent of 2-tert-butylthio-1-methylimidazole.
The invention has the beneficial effects that:
1. the chloroacetaldehyde acetal has relatively low price, and the reaction speed is equivalent to the reaction speed of bromide by adjusting the concentration of methylamine solution.
2. Avoids the generation of byproduct HSCN inevitably during post-treatment when KSCN is adopted in the prior method, and the substance can be rapidly decomposed at normal temperature to generate highly toxic substance HCN, thereby being beneficial to the labor protection of workers.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1:
firstly, adding 249g of chloroacetaldehyde dimethyl acetal and 218g of water into a 1L high-pressure reaction kettle, then introducing 218g of monomethylamine gas, starting stirring, heating to 80-85 ℃, reacting for 16 hours, wherein the GC detection raw material content is less than or equal to 0.5%, cooling, releasing pressure, reducing the temperature to about 20 ℃, adding 100g of dichloromethane each time, extracting for 3 times, combining organic phases, evaporating the solvent, then carrying out vacuum rectification to obtain 202g of a product, wherein the GC content is 96%, and the yield is 85%.
Secondly, 202g of the product, 186g of tert-butyl sulfonitrile and 600mL of toluene are added into a 1L three-necked flask, the mixture is stirred, the temperature is reduced to about 15 ℃, and 12g of boron trifluoride diethyl etherate solution is added dropwise, and the temperature is controlled to be not more than 25 ℃. After the dripping is finished, the temperature is raised to 50-55 ℃ for reaction for 3 hours, the temperature is raised while the reaction is carried out, the solvent is evaporated out under normal pressure until the GC detection raw material disappears, the temperature is reduced to 20 ℃, 20 percent sodium hydroxide is used for adjusting the pH value to 7, 3 x 300g dichloromethane is used for extraction, the organic phases are combined, 100g electronic grade ultrapure water is used for washing for 1 time, the solvent is concentrated, and then the product 240g is distilled out through decompression and distillation, the GC content is 94 percent, and the yield is 83 percent.
And thirdly, adding 240g of the product and 1.2L of toluene into a 2L three-necked bottle under the protection of nitrogen, adding 19g of aluminum trichloride in batches under stirring, stirring at room temperature until the GC controlled raw material completely reacts, filtering out insoluble substances, concentrating the filtrate under reduced pressure until solid is separated out, adding 500g of ethyl acetate, heating to 50 ℃, stirring for 30 minutes, cooling to 10 ℃, centrifuging to obtain a crude product, crystallizing the crude product by using electronic grade ultrapure water to obtain 146g of product, wherein the yield is 91%.
Example 2:
firstly, adding 249g of chloroacetaldehyde dimethyl acetal and 84g of water into a 1L high-pressure reaction kettle, then introducing 156g of monomethylamine gas, starting stirring, heating to 80-85 ℃, reacting for 16 hours, wherein the content of GC detection raw materials is less than or equal to 0.5%, cooling, releasing pressure, reducing the temperature to about 20 ℃, adding 100g of dichloromethane each time, extracting for 3 times, combining organic phases, evaporating a solvent, then carrying out vacuum rectification to obtain 198g of a product, wherein the content of GC is 95%, and the yield is 83%.
Secondly, 198g of the product, 201g of tert-butyl sulfonitrile and 600mL of toluene are added into a 1L three-necked flask, stirring is started, the temperature is reduced to about 15 ℃, 36g of boron trifluoride tetrahydrofuran solution is dropwise added, and the temperature is controlled to be not more than 25 ℃. After the dripping is finished, the temperature is raised to 60-70 ℃ for reaction for 3 hours, the temperature is raised, the reaction is carried out while the solvent is distilled off at normal pressure until the raw material is disappeared by GC detection, the temperature is reduced to 20 ℃, 20% sodium hydroxide is used for adjusting the pH value to 7, 3 x 300g dichloromethane is used for extraction, the organic phases are combined, 100g electronic-grade ultrapure water is used for washing for 1 time, the solvent is concentrated, and then the product 238g is distilled out by decompression and distillation, the GC content is 94%, and the yield is 84%.
And thirdly, adding 238g of the product and 1.2L of dimethylbenzene into a 2L three-neck bottle under the protection of nitrogen, introducing 25g of boron trichloride while stirring, stirring at room temperature until the GC-controlled raw material completely reacts, filtering out insoluble substances, concentrating the filtrate under reduced pressure until solid is separated out, adding 500g of ethyl acetate, heating to 50 ℃, stirring for 30 minutes, cooling to 10 ℃, centrifuging to obtain a crude product, crystallizing the crude product by using electronic grade ultrapure water to obtain 142g of the product, wherein the yield is 89%.
Example 3:
firstly, adding 249g of chloroacetaldehyde dimethyl acetal and 117g of water into a 1L high-pressure reaction kettle, then introducing 218g of monomethylamine gas, starting stirring, heating to 80-85 ℃, reacting for 16 hours, wherein the content of a raw material detected by GC is less than or equal to 0.5%, cooling, releasing pressure, reducing the temperature to about 20 ℃, adding 100g of dichloromethane each time, extracting for 3 times, combining organic phases, evaporating a solvent, then carrying out vacuum rectification to obtain 207g of a product, wherein the content of GC is 96%, and the yield is 87%.
And secondly, adding 207g of the product, 200g of tert-butyl sulfonitrile and 600mL of toluene into a 1L three-necked flask, starting stirring, cooling to about 15 ℃, and dropwise adding 29g of boron trifluoride acetonitrile solution, wherein the temperature is controlled to be not more than 25 ℃. After dripping, the temperature is raised to 60-70 ℃ for reaction for 3 hours, the temperature is raised, the reaction is carried out while the solvent is distilled off at normal pressure until the GC detection raw material disappears, the temperature is reduced to 20 ℃, 20 percent sodium hydroxide is used for adjusting the pH value to 7, 3 x 300g dichloromethane is used for extraction, the organic phases are combined, 100g electronic grade ultrapure water is used for washing for 1 time, the solvent is concentrated, then the product 246g is distilled out by decompression and distillation, the GC content is 94 percent, and the yield is 83 percent.
And thirdly, adding 246g of the product and 1.2L of anisole into a 2L three-necked bottle under the protection of nitrogen, adding 29g of aluminum trichloride in batches under stirring, stirring at room temperature until the GC controlled raw material completely reacts, filtering out insoluble substances, concentrating the filtrate under reduced pressure until solid is separated out, adding 500g of ethyl acetate, heating to 50 ℃, stirring for 30 minutes, cooling to 10 ℃, centrifuging to obtain a crude product, crystallizing the crude product by using electronic grade ultrapure water to obtain 150g of the product, wherein the yield is 91%.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (4)
1. A preparation method of 2-mercapto-1-methylimidazole is characterized by comprising the following steps: step one, performing tank closing reaction on chloroacetaldehyde dimethyl acetal and methylamine water solution at the temperature of 80-85 ℃, and performing reduced pressure rectification to obtain methylamino acetaldehyde dimethyl acetal; in the first step, the ratio of chloroacetaldehyde dimethyl acetal to methylamine is 1: 2.5-3.5;
secondly, performing condensation reaction on methylamino acetaldehyde dimethyl acetal and tert-butyl thionitrile at 50-70 ℃ under the catalysis of boron trifluoride to obtain 2-tert-butylthio-1-methylimidazole; in the second step, the molar ratio of methylamino acetaldehyde dimethyl acetal, tert-butyl sulfur nitrile and boron trifluoride is 1: 0.95-1.05: 0.05-0.15;
adding a catalyst and an organic solvent into 2-tert-butylthio-1-methylimidazole, reacting at normal temperature, filtering, concentrating the filtrate, and recrystallizing with water to obtain 2-mercapto-1-methylimidazole; in the third step, the catalyst is selected from aluminum trichloride or boron trichloride; the addition amount of the catalyst is 0.10-0.15 equivalent of 2-tert-butylthio-1-methylimidazole.
2. The process according to claim 1 for preparing 2-mercapto-1-methylimidazole, which comprises: in the first step, 50-65% concentration methylamine water solution is adopted.
3. The process according to claim 1 for preparing 2-mercapto-1-methylimidazole, which comprises: in the second step, boron trifluoride is boron trifluoride-diethyl ether, boron trifluoride-tetrahydrofuran or boron trifluoride-acetonitrile.
4. The process according to claim 1 for preparing 2-mercapto-1-methylimidazole, which comprises: in the third step, the organic solvent is toluene, xylene or anisole.
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CN107162983A (en) * | 2017-06-12 | 2017-09-15 | 常州市天华制药有限公司 | A kind of synthesis of methimazole and process for purification |
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JPS63290851A (en) * | 1987-05-25 | 1988-11-28 | Daicel Chem Ind Ltd | Production of alkylaminoacetals |
WO2012178015A2 (en) * | 2011-06-24 | 2012-12-27 | Zenobia Therapeutics, Inc. | Lrrk2 inhibitors |
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Patent Citations (6)
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EP1044965A1 (en) * | 1998-09-09 | 2000-10-18 | Nippon Finechemical Co., Ltd. | Process for the preparation of aromatic sulfur compounds |
CN101613320A (en) * | 2009-08-06 | 2009-12-30 | 丹东恒悦新材料有限公司 | 2-substituted imidazole compound and preparation method thereof |
CN103930422A (en) * | 2011-07-19 | 2014-07-16 | 无限药品股份有限公司 | Heterocyclic compounds and uses thereof |
CN103214421A (en) * | 2012-12-11 | 2013-07-24 | 上海博康精细化工有限公司 | Industrialization production method of 2-mercapto-1-methylimidazole |
CN103086977A (en) * | 2013-02-01 | 2013-05-08 | 江苏康乐新材料科技有限公司 | Method for preparing 2-ethyl-4-methylimidazole |
CN107162983A (en) * | 2017-06-12 | 2017-09-15 | 常州市天华制药有限公司 | A kind of synthesis of methimazole and process for purification |
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