CN102924346A - Method for synthesizing methyl sulfone base dibromo toluene - Google Patents
Method for synthesizing methyl sulfone base dibromo toluene Download PDFInfo
- Publication number
- CN102924346A CN102924346A CN201210442127XA CN201210442127A CN102924346A CN 102924346 A CN102924346 A CN 102924346A CN 201210442127X A CN201210442127X A CN 201210442127XA CN 201210442127 A CN201210442127 A CN 201210442127A CN 102924346 A CN102924346 A CN 102924346A
- Authority
- CN
- China
- Prior art keywords
- methylsulfonyl dibromomethylbenzene
- crude product
- methylsulfonyl
- dibromomethylbenzene
- bromine
- 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
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method for synthesizing methyl sulfone base dibromo toluene. The method comprises the following steps of enabling methyl p-tolyl sulfone and bromine to perform thermal reaction for 5-20 hours at the temperature of 50-200 DEG C under the effect of an catalytic agent to obtain liquid crude product methyl sulfone base dibromo toluene, wherein the mole ratio of the methyl p-tolyl sulfone to the bromine is 1: (1-10); and separating the liquid crude product methyl sulfone base dibromo toluene to remove hydrobromic acid produced in the reaction and unreacted bromine to obtain granular solid crude product methyl sulfone base dibromo toluene. The method is short in process flow and mild in reaction condition, the reaction can be easily controlled, industrial production can be easily achieved, no solvent is used, the whole reaction process is free of pollution and emission, and the product yield is as high as 93-98%.
Description
Technical field
The present invention relates to technical field of organic synthesis, be specifically related to a kind of synthetic method to the methylsulfonyl dibromomethylbenzene.
Background technology
Be important organic medical material to the methylsulfonyl dibromomethylbenzene, be the light brown particulate solid, 140～145 ℃ of fusing points, water insoluble, be dissolved in common organic solvents.It is the important intermediate of New-type wide-spectrum microbiotic thiamphenicol, Urfamicin.Because thiamphenicol and derivative glycine ester hydrochloride toxicity is low, side effect is little, curative effect is long, has good anti-microbial effect, and anti-microbial activity is strong more than 6 times than paraxin.Extensively be allowed for abroad the immunosuppressive condition microbiotic and be used as food, fodder additives etc., demand increase year after year.
Thiamphenicol adopts the methylsulfonyl dibromomethylbenzene is synthesized the methylsulfonyl phenyl aldehyde at present, and then the synthetic route that MSM benzene Serine is finally synthesized thiamphenicol; This route raw material is easy to get, and simple to operate, operational path is short, and plant factor and yield are all high than additive method.This method is in labour protection and be lowered into our mask higher productive value is arranged.Therefore present stage, domestic thiamphenicol is synthetic to be adopted the methylsulfonyl dibromomethylbenzene is that the output of raw material method is increasing.Cause the domestic demand that the turnout of methylsulfonyl dibromomethylbenzene can not satisfied market.
Summary of the invention
Technical problem to be solved by this invention is: for the deficiency that prior art exists, provide that a kind of operational path is short, product purity is high, yield is high and free of contamination synthetic method to the methylsulfonyl dibromomethylbenzene.
For solving the problems of the technologies described above, technical scheme of the present invention is:
A kind of synthetic method to the methylsulfonyl dibromomethylbenzene may further comprise the steps:
(1) will to methylsulfonyltoluene and bromine according to the mol ratio of 1:1～10 under 50～200 ℃ temperature condition, under catalyst action, carried out insulation reaction 5～20 hours, obtain liquid crude product to the methylsulfonyl dibromomethylbenzene.
(2) described liquid crude product is separated Hydrogen bromide and the unreacted bromine of removing generation in the reaction to the methylsulfonyl dibromomethylbenzene, obtain the solid-state crude product of particulate state to the methylsulfonyl dibromomethylbenzene.
(3) described solid-state crude product is obtained product to the methylsulfonyl dibromomethylbenzene to the methylsulfonyl dibromomethylbenzene through neutralizing, wash and making with extra care.
Synthetic route is as follows:
Preferably, described catalyzer is selected from one or more in copper and mantoquita, iodine, iron and the molysite.
As further preferred, described mantoquita comprises one or both in cupric chloride, the copper sulfate, and described molysite comprises one or more in iron(ic) chloride, ferric sulfate, iron nitrate and the iron bromide.
Preferably, in the step (1), described reaction mol ratio to methylsulfonyltoluene and bromine is 1:1.5～2.5, and described temperature of reaction is 120～160 ℃, and the insulation reaction time is 10～15 hours.
As a kind of improvement, in the step (2), described liquid crude product is removed Hydrogen bromide and the unreacted bromine that reaction produces through decompression first to the methylsulfonyl dibromomethylbenzene, then described liquid crude product is carried out water to the methylsulfonyl dibromomethylbenzene and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene.
Preferably, described decompression remove Hydrogen bromide and bromine refer to≤-vacuumize 1～5 hour during 0.05MPa.
In the step (3), described in and the time adopt in yellow soda ash, sodium hydroxide, sodium bicarbonate, salt of wormwood and the potassium hydroxide solution one or more.Preferred sodium carbonate solution, the concentration of sodium carbonate solution is 5～10wt%.
Described making with extra care is that then suction filtration, drying obtain product with the methylsulfonyl dibromomethylbenzene is made with extra care in 80～90 ℃ hot water after neutralization, the washing.
Preferably, the add-on of described catalyzer is 0.5～5wt% to methylsulfonyltoluene.
Owing to having adopted technique scheme, the invention has the beneficial effects as follows:
The present invention adopts methylsulfonyltoluene and bromine according to certain mol proportion and certain temperature, under catalyst action, and the reaction preparation is to the methylsulfonyl dibromomethylbenzene, and obtains product to the methylsulfonyl dibromomethylbenzene through purification and refinement treatment.The inventive method operational path is short, and reaction conditions is gentle, and reaction is control easily, is easy to realize suitability for industrialized production, does not adopt any solvent, and whole reaction process is pollution-free, zero release, and product yield is high, can reach 93～98%.
The present invention passes through the two-stage purification process to the crude product that reaction obtains to the methylsulfonyl dibromomethylbenzene, remove Hydrogen bromide and unreacted bromine that reaction produces, elder generation separates through pressure reducing mode removes, then carries out Hydrogen bromide and the unreacted bromine that water absorption processing removal reaction produces, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene, product purity is high after the two-stage purification process, and water is when absorb processing, at purifying product is carried out crystallization in the product, obtain granular product; And product makes with extra care through 80～90 ℃ hot water after neutralization washing again, and the product purity that obtains can reach more than 99.0%.
Embodiment
Further set forth the present invention below in conjunction with specific embodiment.
Embodiment 1
Will to methylsulfonyltoluene and bromine according to the mol ratio of 1:5 under 150 ℃ temperature condition, under the effect of catalyzer copper, carried out insulation reaction 8 hours, obtain liquid crude product to the methylsulfonyl dibromomethylbenzene, the add-on of described catalyzer is the 1wt% to methylsulfonyltoluene.
Described liquid crude product is separated Hydrogen bromide and the unreacted bromine of removing generation in the reaction to the methylsulfonyl dibromomethylbenzene, obtain the solid-state crude product of particulate state to the methylsulfonyl dibromomethylbenzene.
Described solid-state crude product is obtained product to the methylsulfonyl dibromomethylbenzene to the methylsulfonyl dibromomethylbenzene through neutralizing, wash and making with extra care, and the yield of product is 95%, and purity is 99.2%.
Embodiment 2
To join in the reactor methylsulfonyltoluene first, be warmed up to 120 ℃, adding is to the catalyzer cupric chloride of the 0.5wt% of methylsulfonyltoluene, add bromine under the whipped state, mol ratio to methylsulfonyltoluene and bromine is 1:10, carry out insulation reaction 15 hours, and obtained liquid crude product to the methylsulfonyl dibromomethylbenzene.
Open vacuum pump, under-0.05MPa, vacuumize 1.5 hours, Hydrogen bromide and the unreacted bromine that reaction produces removed in decompression, the end of bleeding, described liquid crude product stirred the methylsulfonyl dibromomethylbenzene transfer in the entry, carry out water and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene simultaneously.
Adopt sodium carbonate solution to be neutralized to neutrality to the methylsulfonyl dibromomethylbenzene described solid-state crude product, then the suction filtration after washing is warming up to water lotion 80 ℃ and makes with extra care, and obtains product to the methylsulfonyl dibromomethylbenzene finally by high temperature suction filtration and drying, the yield of product is 95.5%, and purity is 99.35%.
Embodiment 3
To join in the reactor methylsulfonyltoluene first, be warmed up to 160 ℃, adding is to the catalyst sulfuric acid copper of the 1.5wt% of methylsulfonyltoluene, add bromine under the whipped state, mol ratio to methylsulfonyltoluene and bromine is 1:1.5, carry out insulation reaction 10 hours, and obtained liquid crude product to the methylsulfonyl dibromomethylbenzene.
Open vacuum pump, under-0.06MPa, vacuumize 4 hours, Hydrogen bromide and the unreacted bromine that reaction produces removed in decompression, the end of bleeding, described liquid crude product stirred the methylsulfonyl dibromomethylbenzene transfer in the entry, carry out water and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene simultaneously.
Adopt sodium hydroxide solution to be neutralized to neutrality to the methylsulfonyl dibromomethylbenzene described solid-state crude product, then the suction filtration after washing is warming up to water lotion 90 ℃ and makes with extra care, and obtains product to the methylsulfonyl dibromomethylbenzene finally by high temperature suction filtration and drying, the yield of product is 95.5%, and purity is 99.4%.
Embodiment 4
To join in the reactor methylsulfonyltoluene first, be warmed up to 100 ℃, adding is to catalyzer iron and the iron bromide of the 2wt% of methylsulfonyltoluene, add bromine under the whipped state, mol ratio to methylsulfonyltoluene and bromine is 1:2, carry out insulation reaction 12 hours, and obtained liquid crude product to the methylsulfonyl dibromomethylbenzene.
Open vacuum pump, under-0.07MPa, vacuumize 3 hours, Hydrogen bromide and the unreacted bromine that reaction produces removed in decompression, the end of bleeding, described liquid crude product stirred the methylsulfonyl dibromomethylbenzene transfer in the entry, carry out water and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene simultaneously.
Adopt sodium hydrogen carbonate solution to be neutralized to neutrality to the methylsulfonyl dibromomethylbenzene described solid-state crude product, then the suction filtration after washing is warming up to water lotion 85 ℃ and makes with extra care, and obtains product to the methylsulfonyl dibromomethylbenzene finally by high temperature suction filtration and drying, the yield of product is 95.35%, and purity is 99.5%.
Embodiment 5
To join in the reactor methylsulfonyltoluene first, be warmed up to 60 ℃, add the catalyst iodine to the 5wt% of methylsulfonyltoluene, add bromine under the whipped state, mol ratio to methylsulfonyltoluene and bromine is 1:10, carries out insulation reaction 20 hours, obtains liquid crude product to the methylsulfonyl dibromomethylbenzene.
Open vacuum pump, under-0.08MPa, vacuumize 2.5 hours, Hydrogen bromide and the unreacted bromine that reaction produces removed in decompression, the end of bleeding, described liquid crude product stirred the methylsulfonyl dibromomethylbenzene transfer in the entry, carry out water and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene simultaneously.
Adopt solution of potassium carbonate to be neutralized to neutrality to the methylsulfonyl dibromomethylbenzene described solid-state crude product, then the suction filtration after washing is warming up to water lotion 82 ℃ and makes with extra care, and obtains product to the methylsulfonyl dibromomethylbenzene finally by high temperature suction filtration and drying, the yield of product is 95.0%, and purity is 99.2%.
Embodiment 6
To join in the reactor methylsulfonyltoluene first, be warmed up to 200 ℃, adding is to the catalyzer iron(ic) chloride of the 1wt% of methylsulfonyltoluene, add bromine under the whipped state, mol ratio to methylsulfonyltoluene and bromine is 1:1～10, carry out insulation reaction 5～20 hours, and obtained liquid crude product to the methylsulfonyl dibromomethylbenzene.
Open vacuum pump, under-0.08MPa, vacuumize 1～5 hour, Hydrogen bromide and the unreacted bromine that reaction produces removed in decompression, the end of bleeding, described liquid crude product stirred the methylsulfonyl dibromomethylbenzene transfer in the entry, carry out water and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene simultaneously.
Adopt yellow soda ash, sodium hydroxide, yellow soda ash, salt of wormwood and potassium hydroxide solution to be neutralized to neutrality to the methylsulfonyl dibromomethylbenzene described solid-state crude product, the suction filtration after washing, then water lotion being warming up to 80～90 ℃ makes with extra care, obtain product to the methylsulfonyl dibromomethylbenzene finally by high temperature suction filtration and drying, the yield of product is 95%, and purity is 99.2%.
Embodiment 7
To join in the reactor methylsulfonyltoluene first, be warmed up to 90 ℃, adding is to the catalyst sulfuric acid iron of the 2wt% of methylsulfonyltoluene, add bromine under the whipped state, mol ratio to methylsulfonyltoluene and bromine is 1:2.5, carry out insulation reaction 12 hours, and obtained liquid crude product to the methylsulfonyl dibromomethylbenzene.
Open vacuum pump, under-0.09MPa, vacuumize 2.5 hours, Hydrogen bromide and the unreacted bromine that reaction produces removed in decompression, the end of bleeding, described liquid crude product stirred the methylsulfonyl dibromomethylbenzene transfer in the entry, carry out water and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene simultaneously.
Adopt potassium hydroxide solution to be neutralized to neutrality to the methylsulfonyl dibromomethylbenzene described solid-state crude product, then the suction filtration after washing is warming up to water lotion 84 ℃ and makes with extra care, and obtains product to the methylsulfonyl dibromomethylbenzene finally by high temperature suction filtration and drying, the yield of product is 95.1%, and purity is 99.32%.
Embodiment 8
To join in the reactor methylsulfonyltoluene first, be warmed up to 140 ℃, adding is to the catalyzer iron nitrate of the 1.5wt% of methylsulfonyltoluene, add bromine under the whipped state, mol ratio to methylsulfonyltoluene and bromine is 1:3, carry out insulation reaction 15 hours, and obtained liquid crude product to the methylsulfonyl dibromomethylbenzene.
Open vacuum pump, under-0.05MPa, vacuumize 2 hours, Hydrogen bromide and the unreacted bromine that reaction produces removed in decompression, the end of bleeding, described liquid crude product stirred the methylsulfonyl dibromomethylbenzene transfer in the entry, carry out water and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene simultaneously.
Adopt sodium carbonate solution to be neutralized to neutrality to the methylsulfonyl dibromomethylbenzene described solid-state crude product, the concentration of sodium carbonate solution is 8wt%, the suction filtration after washing, then water lotion being warming up to 80 ℃ makes with extra care, obtain product to the methylsulfonyl dibromomethylbenzene finally by high temperature suction filtration and drying, the yield of product is 95.45%, and purity is 99.63%.
Claims (9)
1. synthetic method to the methylsulfonyl dibromomethylbenzene is characterized in that may further comprise the steps:
(1) will to methylsulfonyltoluene and bromine according to the mol ratio of 1:1～10 under 50～200 ℃ temperature condition, under catalyst action, carried out insulation reaction 5～20 hours, obtain liquid crude product to the methylsulfonyl dibromomethylbenzene;
(2) described liquid crude product is separated Hydrogen bromide and the unreacted bromine of removing generation in the reaction to the methylsulfonyl dibromomethylbenzene, obtain the solid-state crude product of particulate state to the methylsulfonyl dibromomethylbenzene;
(3) described solid-state crude product is obtained product to the methylsulfonyl dibromomethylbenzene to the methylsulfonyl dibromomethylbenzene through neutralizing, wash and making with extra care.
2. the synthetic method to the methylsulfonyl dibromomethylbenzene as claimed in claim 1, it is characterized in that: described catalyzer is selected from one or more in copper and mantoquita, iodine, iron and the molysite.
3. the synthetic method to the methylsulfonyl dibromomethylbenzene as claimed in claim 2, it is characterized in that: described mantoquita comprises one or both in cupric chloride, the copper sulfate, described molysite comprises one or more in iron(ic) chloride, ferric sulfate, iron nitrate and the iron bromide.
4. the synthetic method to the methylsulfonyl dibromomethylbenzene as claimed in claim 1, it is characterized in that: in the step (1), described reaction mol ratio to methylsulfonyltoluene and bromine is 1:1.5～2.5, and described temperature of reaction is 120～160 ℃, and the insulation reaction time is 10～15 hours.
5. the synthetic method to the methylsulfonyl dibromomethylbenzene as claimed in claim 1, it is characterized in that: in the step (2), described liquid crude product is removed Hydrogen bromide and the unreacted bromine that reaction produces through decompression first to the methylsulfonyl dibromomethylbenzene, then described liquid crude product is carried out water to the methylsulfonyl dibromomethylbenzene and absorb processing, decrease temperature crystalline obtains the particulate state crude product to the methylsulfonyl dibromomethylbenzene.
6. the synthetic method to the methylsulfonyl dibromomethylbenzene as claimed in claim 5 is characterized in that: described decompression remove Hydrogen bromide and bromine refer to≤-vacuumize 1～5 hour during 0.05MPa.
7. the synthetic method to the methylsulfonyl dibromomethylbenzene as claimed in claim 1 is characterized in that: in the step (3), described in and the time adopt in yellow soda ash, sodium hydroxide, sodium bicarbonate, salt of wormwood and the potassium hydroxide solution one or more.
8. such as the described synthetic method to the methylsulfonyl dibromomethylbenzene of the arbitrary claim of claim 1 to 7, it is characterized in that: described making with extra care is that then suction filtration, drying obtain product with the methylsulfonyl dibromomethylbenzene is made with extra care in 80～90 ℃ hot water after neutralization, the washing.
9. the synthetic method to the methylsulfonyl dibromomethylbenzene as claimed in claim 8 is characterized in that: the add-on of described catalyzer is 0.5～5wt% to methylsulfonyltoluene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210442127.XA CN102924346B (en) | 2012-11-07 | 2012-11-07 | Method for synthesizing methyl sulfone base dibromo toluene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210442127.XA CN102924346B (en) | 2012-11-07 | 2012-11-07 | Method for synthesizing methyl sulfone base dibromo toluene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102924346A true CN102924346A (en) | 2013-02-13 |
| CN102924346B CN102924346B (en) | 2014-08-20 |
Family
ID=47639308
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210442127.XA Active CN102924346B (en) | 2012-11-07 | 2012-11-07 | Method for synthesizing methyl sulfone base dibromo toluene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102924346B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367462A (en) * | 2014-08-20 | 2016-03-02 | 潍坊玉成化工有限公司 | Preparation method of p-methylsulfonylphenylserine copper |
| CN106957250A (en) * | 2016-01-11 | 2017-07-18 | 湖北君尚科技有限公司 | A kind of bromination process to methylsulfonyltoluene |
| CN113149875A (en) * | 2021-04-27 | 2021-07-23 | 浙江嘉福新材料科技有限公司 | Method for preparing p-methylsulfonylbenzaldehyde by continuous flow |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3700736A (en) * | 1969-07-16 | 1972-10-24 | Sumitomo Chemical Co | Preparation of p-methylsulfonyl benzaldehhyde |
| US4849565A (en) * | 1986-07-21 | 1989-07-18 | Kurt Baum | 1,3-diethynyladamantane and methods of polymerization thereof |
| WO2002102810A2 (en) * | 2001-06-14 | 2002-12-27 | Technion Research And Development Foundation Ltd. | Synthesis of (dibromocyclobuta) aromatic compounds |
| JP2003026670A (en) * | 2001-07-16 | 2003-01-29 | Tosoh Corp | Method of production for thiazole derivative |
| EP1559704A1 (en) * | 2004-01-30 | 2005-08-03 | Ethicon, Inc. | Synthesis of 4-substituted phthalaldehyde |
| CN1810774A (en) * | 2005-01-25 | 2006-08-02 | 住友化学株式会社 | A process for producing an aralkyl compound, a dehalogenation method of an aralkyl halide compound and a method for recovering an aralkyl compound |
| CN101265222A (en) * | 2008-04-29 | 2008-09-17 | 南京科邦医药化工有限公司 | Green hydrolysis technique for dibromomethyl-4-methanesulfonyl-benzene |
| CN102020587A (en) * | 2010-11-25 | 2011-04-20 | 大连凯飞精细化工有限公司 | Method for synthesizing 2-methoxy-4-cyano benzaldehyde |
-
2012
- 2012-11-07 CN CN201210442127.XA patent/CN102924346B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3700736A (en) * | 1969-07-16 | 1972-10-24 | Sumitomo Chemical Co | Preparation of p-methylsulfonyl benzaldehhyde |
| US4849565A (en) * | 1986-07-21 | 1989-07-18 | Kurt Baum | 1,3-diethynyladamantane and methods of polymerization thereof |
| WO2002102810A2 (en) * | 2001-06-14 | 2002-12-27 | Technion Research And Development Foundation Ltd. | Synthesis of (dibromocyclobuta) aromatic compounds |
| JP2003026670A (en) * | 2001-07-16 | 2003-01-29 | Tosoh Corp | Method of production for thiazole derivative |
| EP1559704A1 (en) * | 2004-01-30 | 2005-08-03 | Ethicon, Inc. | Synthesis of 4-substituted phthalaldehyde |
| CN1810774A (en) * | 2005-01-25 | 2006-08-02 | 住友化学株式会社 | A process for producing an aralkyl compound, a dehalogenation method of an aralkyl halide compound and a method for recovering an aralkyl compound |
| CN101265222A (en) * | 2008-04-29 | 2008-09-17 | 南京科邦医药化工有限公司 | Green hydrolysis technique for dibromomethyl-4-methanesulfonyl-benzene |
| CN102020587A (en) * | 2010-11-25 | 2011-04-20 | 大连凯飞精细化工有限公司 | Method for synthesizing 2-methoxy-4-cyano benzaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| WAYKOLE LILADHAR等: "Selective Benzylic Bromination of 2一Methylnaphtllalene", 《SYNTH．COMMUN.》 * |
| 程序 等: "液相催化调聚合成卤代烃的催化剂研究进展", 《工业催化》 * |
| 邢其毅 等: "《基础有机化学》", 30 November 1993 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105367462A (en) * | 2014-08-20 | 2016-03-02 | 潍坊玉成化工有限公司 | Preparation method of p-methylsulfonylphenylserine copper |
| CN105367462B (en) * | 2014-08-20 | 2017-11-07 | 潍坊玉成化工有限公司 | A kind of preparation method of pmethylsulfonyl phenyleneserine copper |
| CN106957250A (en) * | 2016-01-11 | 2017-07-18 | 湖北君尚科技有限公司 | A kind of bromination process to methylsulfonyltoluene |
| CN113149875A (en) * | 2021-04-27 | 2021-07-23 | 浙江嘉福新材料科技有限公司 | Method for preparing p-methylsulfonylbenzaldehyde by continuous flow |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102924346B (en) | 2014-08-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6719527B2 (en) | Method for preparing azoxystrobin intermediate | |
| CN103664511A (en) | Preparation method of 5-bromo-1,3-dichloro-2-fluorobenzene | |
| CN102924346B (en) | Method for synthesizing methyl sulfone base dibromo toluene | |
| CN103058899B (en) | Synthetic method for methyl-sulfuryl benzaldehyde | |
| CN101648895A (en) | Preparing method of para methyl p-tolyl sulfone | |
| CN108558607B (en) | Efficient synthesis method of o-fluorophenol | |
| CN104119243B (en) | A kind of energy-saving clean production method of iminodiethanoic acid | |
| CN101565400B (en) | Preparation method of 4-amino-3, 5, 6-chloropyridine-2-methanoic acid | |
| CN102108063A (en) | Method for preparing maleic hydrazide | |
| CN102417472B (en) | Preparation method of florfenicol | |
| CN104529934B (en) | The synthetic method of a kind of nicotinic insecticide clothianidin | |
| CN101735154B (en) | Preparation method of maleic hydrazide | |
| CN102285937A (en) | Method for synthesizing febuxostat | |
| CN103012473B (en) | A kind of synthetic method of pmida98 | |
| CN102464699A (en) | Preparation method of carbenoxolone sodium | |
| CN109575019B (en) | Preparation method of 5-bromo-7-azaindole | |
| CN103665063A (en) | Method for preparing isopropyl-beta-D-isopropylthiogalactoside | |
| CN103709210B (en) | The preparation technology of isopropyl-β-D-thiogalactoside | |
| CN103694285B (en) | A kind of preparation method of isopropyl-β-D-thiogalactoside(IPTG) | |
| CN100439511C (en) | Process for catalytic extraction of yam saponin by using modified cellulase | |
| CN105017232A (en) | Synthesis method of triazole bactericide | |
| CN103694284B (en) | A kind of preparation technology of isopropyl-β-D-thiogalactoside(IPTG) | |
| CN106117212A (en) | A kind of sldenafil synthesis technique of improvement | |
| CN105175320A (en) | Preparation method of 3-hydroxypyridine | |
| CN104945430B (en) | The preparation method of polyalcohol monomethyl ether trimethyl silane |
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 |