CN1995014A - Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid - Google Patents

Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid Download PDF

Info

Publication number
CN1995014A
CN1995014A CNA2006101511828A CN200610151182A CN1995014A CN 1995014 A CN1995014 A CN 1995014A CN A2006101511828 A CNA2006101511828 A CN A2006101511828A CN 200610151182 A CN200610151182 A CN 200610151182A CN 1995014 A CN1995014 A CN 1995014A
Authority
CN
China
Prior art keywords
methylsulfonyl toluene
nitro
acid catalyst
solid super
methylsulfonyl
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.)
Pending
Application number
CNA2006101511828A
Other languages
Chinese (zh)
Inventor
孙志忠
侯艳君
高金胜
张彦坤
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.)
Heilongjiang University
Original Assignee
Heilongjiang University
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 Heilongjiang University filed Critical Heilongjiang University
Priority to CNA2006101511828A priority Critical patent/CN1995014A/en
Publication of CN1995014A publication Critical patent/CN1995014A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The invention discloses a making method of 2-nitro-4-thiotoluene catalyzed by solid hyper-strong acid, which comprises the following steps: adding concentrated nitric acid in the ice bath cooling reacting bottle; adding solid hyperstrong acid catalyst; dripping acetic anhydride; stirring 20-60min; dripping organic solvent with p-thiotoluene; stirring 2-10h; filtering to recycle solid hyperstrong catalyst; decompressing; rectifying filtrate; recycling organic solvent; cooling; adding a little of water; filtering; washing solid; drying to obtain the 2-nitro-4-thiotoluene; rectifying the filtrate to recycle acetate.

Description

The method for preparing 2-nitro-4-methylsulfonyl toluene with solid super acid catalyst
Technical field
The present invention relates to a kind of preparation method of nitro-compound, be specifically related to a kind of with solid super-strong acid as catalyzer, catalytic nitration prepares the nitrated method of 2-nitro-4-methylsulfonyl toluene to methylsulfonyl toluene.
Background technology
2-nitro-4-methylsulfonyl toluene is important organic synthesis intermediate, is applied in the production of dyestuff, medicine and agricultural chemicals.Particularly it is as the intermediate of new and effective corn field herbicide mesotrione (mesotrion), and demand constantly increases.Present existing preparation method adopts to be raw material to methylsulfonyl toluene more, utilizes nitration mixture to carry out nitrated method (US5424481; Fine-chemical intermediate, 2005,32 (2): 502; The Hebei chemical industry, 2005,5:43-45), the shortcoming of this method is in the mixed acid nitrification process because a large amount of vitriol oil and nitric acid of using, not only serious to equipment corrosion, and product can produce a large amount of useless diluted acid water, difficult treatment when aftertreatment, environmental pollution is serious, therefore the application of this method is restricted.In recent years with SO 4 2-/ MxO yUse at catalytic field for the solid super-strong acid of feature and to have obtained broad research, because solid super-strong acid has the acidity stronger than 100% sulfuric acid, and have the catalytic activity height, high temperature resistant, preparation is easy, be easy to separate and reusable, advantage such as environmental pollution is little, at present in the preparation process of organic acid acetic, obtain widespread use, and demonstrated very high catalytic activity.But the research of solid super-strong acid in nitration reaction is less, and mainly concentrates on (fiery explosive journal, 2002,25 (1): 61-63 in the nitrated research of a substituted arene; Fine-chemical intermediate .2006,36 (2): 53-55), this research expectation with the solid super strong acid substitution vitriol oil as the nitration reaction catalyzer, thereby reduce disposal of pollutants, improve conversion rate of products and yield, and catalyzer can be recycled.
Summary of the invention
The objective of the invention is existing there is big, the with serious pollution problem of sulfuric acid consumption in methylsulfonyl methylbenzene nitration technology, a kind of method for preparing 2-nitro-4-methylsulfonyl toluene with solid super acid catalyst is provided in order to solve.
The step of method that the present invention prepares 2-nitro-4-methylsulfonyl toluene is as follows: a, add and the concentrated nitric acid that to the methylsulfonyl toluene mole ratio is 1～1.5: 1 in ice bath cooling reaction flask, add the solid super acid catalyst of 10%～80% pair of methylsulfonyl toluene by weight again; B, to drip in reaction flask with mol ratio to methylsulfonyl toluene be 1～1.5: 1 acetic anhydride again, and temperature of reaction is 0～20 ℃, stirs 20～60 minutes; C, drip the organic solvent contain methylsulfonyl toluene again in reaction flask, temperature of reaction is-10～60 ℃, and stirring reaction 2～20h uses the high pressure liquid chromatograph monitoring reaction, when nearly 100% the time to the transformation efficiency of methylsulfonyl toluene, and stopped reaction; D, the reacting liquid filtering that will handle through above-mentioned steps, the solid solvent wash has obtained solid super acid catalyst; E, the solution after steps d is handled reclaim organic solvent with vacuum distillation method; H, the solution after step e distillation add less water again through cooling, and the solid after the filtration is through washing, and drying promptly obtains 2-nitro-4-methylsulfonyl toluene; F, the solution after step h filters reclaim acetic acid with the distillatory method again.
Solid super acid catalyst in the inventive method is SO 4 2-/ ZrO 2, SO 4 2-/ TiO 2, S 2O 8 2-/ ZrO 2, S 2O 8 2-/ TiO 2, SO 4 2-/ ZrO 2-Al 2O 3, SO 4 2-/ ZrO 2-SiO 2, S 2O 8 2-/ ZrO 2-Al 2O 3Or S 2O 8 2-/ ZrO 2-SiO 2
The present invention's transformation efficiency to methylsulfonyl toluene in reaction process is 100%, and product yield is 95%～98%, detects purity greater than 99% with HPLC, 116～117 ℃ of fusing points.
In the method for the present invention, reaction formula is as follows:
The inventive method, not only method is simple, the reaction conditions gentleness, and be recyclable solid super acid catalyst and can be repeatedly used that product can obtain non-pollutant discharge after the reaction end behind simple recovery solvent through simple filtration.
Method of the present invention has the advantage that catalytic reaction activity height, easy and simple to handle, product are easy to separate, catalyzer is reusable and environmental pollution is little, is suitable for suitability for industrialized production.
Embodiment
Embodiment one: the step that present embodiment prepares 2-nitro-4-methylsulfonyl toluene process is as follows: a, add in ice bath cooling reaction flask and the concentrated nitric acid that to the methylsulfonyl toluene mole ratio is 1～1.5: 1, add the solid super acid catalyst of 10%～80% pair of methylsulfonyl toluene by weight again; B, to drip in reaction flask with mol ratio to methylsulfonyl toluene be 1～1.5: 1 acetic anhydride again, and temperature of reaction is 0～20 ℃, stirs 20～60 minutes; C, drip the organic solvent contain methylsulfonyl toluene again in reaction flask, temperature of reaction is-10～60 ℃, and stirring reaction 2～20h uses the high pressure liquid chromatograph monitoring reaction, when nearly 100% the time to the transformation efficiency of methylsulfonyl toluene, and stopped reaction; D, the reacting liquid filtering that will handle through above-mentioned steps, the solid solvent wash has obtained solid super acid catalyst; E, the solution after steps d is handled reclaim organic solvent with vacuum distillation method; H, the solution after step e distillation add less water again through cooling, and the solid after the filtration is through washing, and drying promptly obtains 2-nitro-4-methylsulfonyl toluene; F, the solution after step h filters reclaim acetic acid with the distillatory method again.
Present embodiment transformation efficiency to methylsulfonyl toluene in reaction process is 100%, and product yield is 95%～98%, detects purity greater than 99% with HPLC, 116～117 ℃ of fusing points.
Embodiment two: present embodiment temperature of reaction in step c is 10～40 ℃.Other is identical with embodiment one.
Embodiment three: the organic solvent among the present embodiment step c is methylene dichloride, ethylene dichloride, chloroform or tetracol phenixin.Other is identical with embodiment one.
Embodiment four: the consumption of the organic solvent among the present embodiment step c is to 2～5 times of methylsulfonyl toluene by weight.Other is identical with embodiment one.
Embodiment five: the consumption of the organic solvent among the present embodiment step c is to 3 times of methylsulfonyl toluene by weight.Other is identical with embodiment one.
Embodiment six: among the present embodiment step a concentrated nitric acid be 1.2: 1 to the methylsulfonyl toluene mole ratio.Other is identical with embodiment one.
Embodiment seven: among the present embodiment step a concentrated nitric acid be 1.3: 1 to the methylsulfonyl toluene mole ratio.Other is identical with embodiment one.
Embodiment eight: among the present embodiment step b acetic anhydride be 1～1.2: 1 to the mol ratio of methylsulfonyl toluene.Other is identical with embodiment one.
Embodiment nine: among the present embodiment step b acetic anhydride be 1～1.3: 1 to the mol ratio of methylsulfonyl toluene.Other is identical with embodiment one.
Embodiment ten: the solid super acid catalyst of present embodiment is SO 4 2-/ ZrO 2, SO 4 2-/ TiO 2, S 2O 8 2-/ ZrO 2, S 2O 8 2-/ TiO 2, SO 4 2-/ ZrO 2-Al 2O 3, SO 4 2-/ ZrO 2-SiO 2, S 2O 8 2-/ ZrO 2-Al 2O 3Or S 2O 8 2-/ ZrO 2-SiO 2
Embodiment 11: the preparation method of the solid super acid catalyst of using in the reaction in the present embodiment is as follows: one, with concentration be salts solution hydrolysis under alkaline condition of Zr, Ti or the Al of 0.25-1.5mol/L, again through ageing under 60～90 ℃ of conditions, filter, deionized water wash obtains corresponding oxyhydroxide or oxide compound after the oven dry; Two, handle the afterreaction thing through step 1 and in 0.3～2mol/L sulphuric acid soln or in 0.5～3mol/L ammonium persulfate solution, flood 0.5-4h; Three, handle the afterreaction thing through step 2 and directly dry, roasting 2～5h in 400～800 ℃ of air promptly obtains strong solid acid catalyst again.
What present embodiment obtained is single solid super acid catalyst.
Embodiment 12: present embodiment and embodiment 11 are different be the preparation method of solid super acid catalyst in step 3 after step 2 is handled afterreaction thing filtration drying, roasting 2～5h obtains solid super acid catalyst in 400～800 ℃ of air.Other is identical with embodiment 11.
Embodiment 13: present embodiment is different with embodiment 11 and 12 be the preparation method of solid super acid catalyst in step 1 with a kind of hydrolysis under alkaline condition respectively in the salts solution of the Zr solution of concentration 0.5mol/L and Ti, Si and Al, two kinds of hydrolyzates are mixed, again through ageing under 60～90 ℃ of conditions, filter, deionized water wash obtains corresponding complex hydroxide or oxide compound after the oven dry.Other is identical with embodiment 11 and 12.
What present embodiment obtained is the compound solid super acid catalyst.
Embodiment 14: Zr and Ti, Si or Al mol ratio are 1: 1～1.5 in the present embodiment.Other is identical with embodiment ten.
Embodiment 15: the step of present embodiment method is as follows: a, adding and the concentrated nitric acid that to the methylsulfonyl toluene mole ratio is 1.1: 1 in ice bath cooling reaction flask add 1.5g SO again 4 2-/ ZrO 2Solid super acid catalyst; B, to drip in reaction flask with mol ratio to methylsulfonyl toluene be 1.1: 1 acetic anhydride again, and temperature of reaction is 0～20 ℃, stirs 20～60 minutes; C, Dropwise 5 .1g is to the dichloroethane solution 15～25mL of methylsulfonyl toluene in reaction flask again, and temperature of reaction is 10～40 ℃, and stirring reaction 10h uses the high pressure liquid chromatography monitoring reaction, when nearly 100% the time to the transformation efficiency of methylsulfonyl toluene, and stopped reaction; D, the reacting liquid filtering that will handle through above-mentioned steps, the solid solvent wash has obtained solid super acid catalyst; E, the solution after steps d is handled reclaim organic solvent with distillating method; H, the solution after step e distillation add less water again through cooling, and the solid after the filtration is through washing, and drying promptly obtains 2-nitro-4-methylsulfonyl toluene; F, the solution after step h filters reclaim acetic acid with the distillatory method again.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.1g, yield 95%, and detecting purity with HPLC is 99%, 116～117 ℃ of fusing points.
Embodiment 16: that present embodiment and embodiment 15 are different is SO 4 2-/ ZrO 2The consumption 2.0g of solid super-strong acid.Other is identical with embodiment 15.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.2g, and yield is 96%, and detecting purity with HPLC is 99.4%, 116～117 ℃ of fusing points.
Embodiment 17: that present embodiment and embodiment 15 are different is SO 4 2-/ ZrO 2The consumption of solid super-strong acid is 3.0g.Other is identical with embodiment 15.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.3g, yield 98%, and detecting purity with HPLC is 99.6%, 116～117 ℃ of fusing points.
Embodiment 18: present embodiment and embodiment 17 are different be concentrated nitric acid with to the mol ratio of methylsulfonyl toluene 1.5: 1.Other is identical with embodiment 17.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.1g, yield 95%, and detecting purity with HPLC is 99.6%, fusing point 116-117 ℃.
Embodiment 15: what present embodiment and embodiment 15 were different is to adopt S 2O 8 2-/ ZrO 2Solid super-strong acid, consumption are 3.0g.Other is identical with embodiment 15.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.1g, and yield 95% obtains product 2-nitro-4-methylsulfonyl toluene 6.1g, yield 95%, and detecting purity with HPLC is 99%, 116～117 ℃ of fusing points.
Embodiment 16: what present embodiment and embodiment 15 were different is to adopt S 2O 8 2-/ ZrO 2-SiO 2Solid super-strong acid, wherein the mol ratio of Zr and Si is 1: 1, consumption 3.0g.Other is identical with embodiment 15.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.1g, and yield 95% detects purity 99.3%, 116～117 ℃ of fusing points with HPLC.
Embodiment 17: what present embodiment and embodiment 15 were different is to adopt SO 4 2-/ TiO 2Solid super-strong acid, consumption are 3.0g.Other is identical with embodiment 15.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.1g, yield 95%, and detecting purity with HPLC is 99.3%, 116～117 ℃ of fusing points.
Embodiment 18: what present embodiment and embodiment 15 were different is to adopt SO 4 2-/ ZrO 2-Al 2O 3Solid super-strong acid, wherein the mol ratio of Zr and Al is 1: 1, consumption is 3.0g.Other is identical with embodiment 15.
Present embodiment obtains 2-nitro-4-methylsulfonyl toluene 6.2g, yield 96%, and detecting purity with HPLC is 99.3%, 116～117 ℃ of fusing points.

Claims (10)

1, a kind of method for preparing 2-nitro-4-methylsulfonyl toluene with solid super acid catalyst, the method steps that it is characterized in that it is as follows: a, add in ice bath cooling reaction flask and the concentrated nitric acid that to the methylsulfonyl toluene mole ratio is 1～1.5: 1, add the solid super acid catalyst of 10%～80% pair of methylsulfonyl toluene by weight again; B, to drip in reaction flask with mol ratio to methylsulfonyl toluene be 1～1.5: 1 acetic anhydride again, and temperature of reaction is 0～20 ℃, stirs 20～60 minutes; C, drip the organic solvent contain methylsulfonyl toluene again in reaction flask, temperature of reaction is-10～60 ℃, and stirring reaction 2～20h uses the high pressure liquid chromatography monitoring reaction, when nearly 100% the time to the transformation efficiency of methylsulfonyl toluene, and stopped reaction; D, the reacting liquid filtering that will handle through above-mentioned steps, solid solvent wash, the solid super acid catalyst that obtains reclaiming; E, the solution after steps d is handled reclaim organic solvent with vacuum distillation method; H, the solution after step e distillation add less water again through cooling, filter, and solid is through washing, and drying promptly obtains 2-nitro-4-methylsulfonyl toluene; F, the solution after step h filters reclaim acetic acid with the distillatory method again.
2, according to claim 1ly prepare the method for 2-nitro-4-methylsulfonyl toluene, it is characterized in that temperature of reaction is 10～40 ℃ in step c with solid super acid catalyst.
3, according to claim 1ly prepare the method for 2-nitro-4-methylsulfonyl toluene, it is characterized in that the organic solvent among the step c is methylene dichloride, ethylene dichloride, chloroform or tetracol phenixin with solid super acid catalyst.
4, according to claim 1ly prepare the method for 2-nitro-4-methylsulfonyl toluene with solid super acid catalyst, the consumption that it is characterized in that the organic solvent among the step c is to 2～5 times of methylsulfonyl toluene by weight.
5, according to claim 1ly prepare the method for 2-nitro-4-methylsulfonyl toluene with solid super acid catalyst, the consumption that it is characterized in that the organic solvent among the step c is to 3 times of methylsulfonyl toluene by weight.
6, according to claim 1ly prepare the method for 2-nitro-4-methylsulfonyl toluene, it is characterized in that among the step a concentrated nitric acid and be 1.2: 1 the methylsulfonyl toluene mole ratio with solid super acid catalyst.
7, according to claim 1ly prepare the method for 2-nitro-4-methylsulfonyl toluene, it is characterized in that among the step a concentrated nitric acid and be 1.3: 1 the methylsulfonyl toluene mole ratio with solid super acid catalyst.
8, a kind of solid super acid catalyst according to claim 1 prepares the method for 2-nitro-4-methylsulfonyl toluene, it is characterized in that acetic anhydride among the step b and mol ratio to methylsulfonyl toluene are 1.2: 1.
9, a kind of solid super acid catalyst according to claim 1 prepares the method for 2-nitro-4-methylsulfonyl toluene, it is characterized in that acetic anhydride among the step b and mol ratio to methylsulfonyl toluene are 1.3: 1.
10, according to claim 1ly prepare the method for 2-nitro-4-methylsulfonyl toluene, it is characterized in that solid super acid catalyst is SO with solid super acid catalyst 4 2-/ ZrO 2, SO 4 2-/ TiO 2, S 2O 8 2-/ ZrO 2, S 2O 8 2-/ TiO 2, SO 4 2-/ ZrO 2-Al 2O 3, SO 4 2-/ ZrO 2-SiO 2, S 2O 8 2-/ ZrO 2-Al 2O 3Or S 2O 8 2-/ ZrO 2-SiO 2
CNA2006101511828A 2006-12-21 2006-12-21 Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid Pending CN1995014A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2006101511828A CN1995014A (en) 2006-12-21 2006-12-21 Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2006101511828A CN1995014A (en) 2006-12-21 2006-12-21 Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid

Publications (1)

Publication Number Publication Date
CN1995014A true CN1995014A (en) 2007-07-11

Family

ID=38250234

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2006101511828A Pending CN1995014A (en) 2006-12-21 2006-12-21 Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid

Country Status (1)

Country Link
CN (1) CN1995014A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093222A (en) * 2010-12-23 2011-06-15 南京大学扬州化学化工研究院 Method for performing toluene selective nitration under catalysis of solid acid catalyst SO42-/TiO2-HNbMoO6
CN103274942A (en) * 2013-06-28 2013-09-04 厦门大学 Method for preparing ethyl levulinate based on solid superacid catalysis and furfuryl alcohol alcoholysis
CN108940312A (en) * 2018-07-10 2018-12-07 常州大学 A kind of S2O82-/ZrO2-SiO2The preparation method and applications of solid acid catalyst
CN115028558A (en) * 2022-06-13 2022-09-09 湖北广富林生物制剂有限公司 Preparation method of o-nitro-p-methylsulfonyl toluene

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102093222A (en) * 2010-12-23 2011-06-15 南京大学扬州化学化工研究院 Method for performing toluene selective nitration under catalysis of solid acid catalyst SO42-/TiO2-HNbMoO6
CN103274942A (en) * 2013-06-28 2013-09-04 厦门大学 Method for preparing ethyl levulinate based on solid superacid catalysis and furfuryl alcohol alcoholysis
CN108940312A (en) * 2018-07-10 2018-12-07 常州大学 A kind of S2O82-/ZrO2-SiO2The preparation method and applications of solid acid catalyst
CN115028558A (en) * 2022-06-13 2022-09-09 湖北广富林生物制剂有限公司 Preparation method of o-nitro-p-methylsulfonyl toluene

Similar Documents

Publication Publication Date Title
CN100509750C (en) Process for continuously preparing nitro-xylene isomer monomer
CN101811925B (en) Preparation method of paraxylene cyclic dimer
CN102584650A (en) Preparation method of 2-nitro-4-methylsulphonylbenzoic acid
CN1995014A (en) Method for preparing 2-nitro-4-methyl p-tolyl sulfone using solid superstrong acid
CN108043456B (en) Polyacid ionic liquid catalyst, preparation method and method for preparing cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate with polyacid ionic liquid catalyst
CN101724174A (en) Method for preparing anti-aging agent RD
CN102757346A (en) Preparation method of dimethyl fumarate
CN105503513A (en) Method for catalytically synthesizing 4,4'-bischloromethylbiphenyl by using silicon dioxide-loaded phosphotungstic acid
CN104262109B (en) A kind of synthetic method of resorcinol
CN103724167B (en) Environment-friendly synthesis method of high-yield perfluoromethylvinyl ether (PMVE)
CN102838487A (en) Synthesis method of 2-ethylhexyl salicylate
CN101397293B (en) Green nitration method based on ion liquid catalysis
CN101434539B (en) Preparation of benzyl acetate
CN103709010B (en) A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method
CN116328790A (en) Preparation method of solid acid catalyst and application of solid acid catalyst in diethylene glycol dibenzoate synthesis
CN102001999B (en) Process for directly synthesizing caprolactam from cyclohexanone and hydroxylamine
CN110526806A (en) Method for preparing acetophenone compounds by catalyzing phenylacetylene with solid acid
CN102850304A (en) Furfural preparation method by using complex perovskites for one-step hydrolysis of xylan
CN110330428B (en) Method for preparing diisobutyl phthalate
CN102850299B (en) Preparation method for (methyl)glycidyl acrylate
CN112142615B (en) Preparation method of isophthalimide
CN106631651A (en) Preparation method of benzyl methylbenzene
CN106673952A (en) Method for catalytic synthesis of benzyl toluene by activated clay-loaded ferric trichloride (FeCl3) solid acid catalyst
CN103130755A (en) Method for preparing furfural through catalytic conversion of xylose by acid photocatalyst under ultraviolet light
CN101857579B (en) Synthesis method of 2-amino-5,6-dichlorobenzothiazole

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication