CN102302948A - Benzenesulfonic acid catalyst supported on silica gel, as well as preparation and application thereof - Google Patents
Benzenesulfonic acid catalyst supported on silica gel, as well as preparation and application thereof Download PDFInfo
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- CN102302948A CN102302948A CN201110167042A CN201110167042A CN102302948A CN 102302948 A CN102302948 A CN 102302948A CN 201110167042 A CN201110167042 A CN 201110167042A CN 201110167042 A CN201110167042 A CN 201110167042A CN 102302948 A CN102302948 A CN 102302948A
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Abstract
The invention discloses a benzenesulfonic acid catalyst supported on silica gel, which is prepared by adopting silica gel to react with thionyl chloride, phenol and chlorosulfonic acid sequentially. In the catalyst, the silica gel and benzenesulfonic acid are bonded in a covalent bond mode, so that the supporting capacity is stable, and the supporting capacity of the benzenesulfonic acid is about 2.25mmol/g in the benzenesulfonic acid catalyst supported on silica gel through analysis and calculation. Experiments prove that: the prepared catalyst has efficient catalytic activity to two kinds of atom economic reactions, namely Beckmann rearrangement reaction and Claisen rearrangement reaction, is non-toxic, harmless and noncorrosive, is easily separated, can be recycled, and accords with green and environmentally-friendly national industrial policy.
Description
Technical field
The invention belongs to chemical technology field, relate to a kind of supported on silica-gel type benzene sulfonic acid Preparation of catalysts method; The present invention also relates to the application of this catalyst in the Claisen rearangement reaction of the Beckmann rearrangement of ketoxime and pi-allyl aryl ether simultaneously.
Background technology
Benzene sulfonic acid often is used as catalyst as a kind of liquid acid, and it has very high activity, and extensive applicability is arranged.But it has the common shortcoming of traditional liquid acid, accomplishes like reaction that rear catalyst is difficult to separate, very strong corrosivity, environment is polluted etc.In today of green chemical industry technology fast development; Will certainly bring very big harm with simple liquid benzene sulfonic acid to environment as the catalyst chemical reaction, therefore develop that nontoxic, harmless, no burn into is prone to reclaim, reusable environment-friendly catalyst will seem necessity very.
Beckmann rearrangement refers to that aldoxime or ketoxime generate the nucleophilic rearangement reaction of N substituted amide under acid catalysis, and this is reflected at has important application in the industry, and cyclohexanone and azanol reaction obtain the rearrangeable caprolactam that obtains behind the cyclohexanone oxime, and this is the monomer of nylon-6.The present catalyst that adopts mainly contains Bronsted acid such as sulfuric acid, polyphosphoric acids and can produce the phosphorus pentachloride of strong acid, phosphorus trichloride, benzene sulfonyl chloride, thionyl chloride etc.; These catalyst are the liquid acid with severe corrosive; And be difficult to from system, separate after the reaction; More can't recycle, not meet environmental requirement.
The Claisen rearangement reaction of pi-allyl aryl ether is that pi-allyl aryl ether is 200 ℃ of high temperature (>) rearrangement reaction of generation down, product is an allyl phenol.Normal lewis acid and the bronsted acid as catalyst such as sulfuric acid, trifluoroacetic acid such as boron chloride, alchlor, titanium tetrachloride, butter of tin of adopting of the reaction of Claisen rearangement at present; The unstable facile hydrolysis that these catalyst have; The corrosivity that has is strong; They are difficult to from system, separate after reaction; More can't recycle, not meet environmental requirement.
Summary of the invention
The objective of the invention is provides a kind of supported on silica-gel type benzene sulfonic acid catalyst to the problem that exists in the prior art.
Another object of the present invention provides a kind of supported on silica-gel type benzene sulfonic acid Preparation of catalysts method.
A further object of the invention just provides a kind of supported on silica-gel type benzene sulfonic acid catalyst in the Beckmann rearrangement of ketoxime and the application in the Claisen rearangement reaction at pi-allyl aryl ether.
Supported on silica-gel type benzene sulfonic acid Preparation of catalysts method of the present invention comprises following processing step:
(1) the muriatic preparation of silica gel
The silica gel of drying is mixed with 1:2 ~ 1:4 weight ratio with thionyl chloride, in 75 ~ 85 ℃ of back flow reaction 20 ~ 24 h; Filter, the gained solid product fully washs with carrene, and vacuum drying obtains faint yellow silica gel chloride solids product;
(2) preparation of supported on silica-gel benzene product
Silica gel chloride and phenol are joined in the carrene stirring and refluxing 36 ~ 48 h with the weight ratio of 1:0.3 ~ 1:0.5; Filter, the gained solid product fully washs with carrene, and vacuum drying obtains supported on silica-gel benzene product;
(3) preparation of supported on silica-gel benzene sulfonic acid
The dichloromethane solution of chlorosulfonic acid is joined in the carrene suspension that contains supported on silica-gel benzene, at room temperature stir 4 ~ 8 h; The gained mixture filters, and solid fully washs with carrene, and vacuum drying obtains supported on silica-gel benzene sulfonic acid product; The weight ratio of said chlorosulfonic acid and supported on silica-gel benzene is 1:2 ~ 1:3.
Said silica gel is macro porous silica gel, silochrom, Type B silica gel or Kiselgel A.
The silica gel that has high surface area in the structure of the supported on silica-gel benzene sulfonic acid of the present invention preparation makes silicon link to each other with covalent bond with benzene sulfonic acid through the oxo bridge on surface; This combination bond energy is very high; Therefore structure is very stable; Supported quantity is very high simultaneously; Through analyzing and calculating, the amount of supported on silica-gel benzene sulfonic acid is 2.18 ~ 2.31 mmol/g; In addition the benzene sulfonic acid active group with the covalent bond form with after carrier silica gel combines, the loss that no longer in the process of common silica gel absorbent-type catalyst, comes off at catalyzed chemical reaction, therefore reclaim with recycling in understand the catalytic activity of maintenance stability and high efficiency.
The catalytic activity of the supported on silica-gel type benzene sulfonic acid catalyst of the present invention's preparation has obtained checking through two types of Atom economy reactions.
1, Beckmann rearrangement
Acetoxime, 2-diacetylmonoxime, cyclopentanone oxime, cyclohexanone oxime, acetophenone oxime or diphenyl-ketoxime are joined in the dichloroethanes with the mol ratio of supported on silica-gel benzene sulfonic acid with 1:0.20 ~ 1:0.25 respectively, and reaction is 5 ~ 6 minutes under the microwave radiation condition; After reacting end, filter, the dichloroethanes of draining in the filtrating promptly gets thick product, and thick product gets the pure article of acid amides behind column chromatography or recrystallization, and productive rate reaches 87 ~ 99%.
2, Claisen rearangement reaction
Allyl phenyl ether, pi-allyl p-tolyl ether, pi-allyl p-methoxyphenyl ether, pi-allyl rubigan ether, pi-allyl p-nitrophenyl ether, pi-allyl 1-naphthyl ether or pi-allyl 2-naphthyl ether are fully ground after with the mixed in molar ratio of 1:0.1～1:0.2 with the supported on silica-gel benzene sulfonic acid respectively, under the microwave radiation condition, reacted 6 ~ 8 minutes then; After reaction finished, reactant mixture dissolved with carrene, filtered, and evaporated the carrene in the filtrating, and residue is recrystallized or uses column chromatography with ether and obtains allyl phenol, and productive rate reaches 93 ~ 99%.
The present invention compares with existing correlation technique and has the following advantages:
1, the supported on silica-gel type benzene sulfonic acid catalyst of the present invention preparation, the phenyl ring of benzene sulfonic acid is through oxygen and the silica gel form bonding with covalent bond, and supported quantity is very stable.
2, the catalyst of the present invention's preparation is compared with traditional liquid benzene sulfonic acid catalyst, and nontoxic, harmless, no burn into is prone to recovery, reusable, environmentally friendly, has adaptability widely.
3, the present invention is raw materials used cheap and easy to get, and preparation technology is simple, and reaction condition is gentle, and cost is low, and productive rate is high, for industrial-scale production has been created good condition.
4, the supported on silica-gel type benzene sulfonic acid catalyst of gained of the present invention is suitable with the liquid benzene sulfonic acid catalyst to the catalytic activity of two types of Atom economy reaction-Beckmann rearrangements and Claisen rearangement reaction; But catalyst is easily separated; Can be recycled, meet the national industrial policies of environmental protection.
The specific embodiment
Through specific embodiment the application in Preparation of catalysts method of the present invention and Beckmann rearrangement, the Claisen rearangement reaction is further specified below.
The preparation of embodiment one, supported on silica-gel benzene sulfonic acid
The muriatic preparation of silica gel: take by weighing 5 g macro porous silica gels, place muffle furnace, behind 120 ℃ of drying 8 h, join in the reactor that reflux condensing tube and drying tube be housed; In container, add 10 mL thionyl chlorides, in 80 ℃ of 24 h that reflux, the color of system becomes yellow in the course of reaction, and As time goes on color is constantly deepened in the oil bath.After reaction finishes, filter, the gained solid product fully washs three times with carrene, remove desolvate the back in vacuum drying chamber in 60 ℃ of drying 10 h, obtain faint yellow solid product 5.3 g.Through analyzing and calculating, the supported quantity of Cl is 2.43 mmol/g in the silica gel chloride.
The preparation of supported on silica-gel benzene: with silica gel chloride (5.3 g, immobilized chlorine dose is 0.013 mol), phenol (2.0 g, 0.021 mol) joins in the carrene (30 mL), and 48 h then under agitation reflux; Filter, the gained solid fully washs 3 times with carrene, then in vacuum drying chamber in 60 ℃ of drying 12 h, obtain product 6.2 g.Through analyzing and calculating, the amount of supported on silica-gel benzene is 2.40 mmol/g.IR?(KBr):?680,?1103?cm
-1。
The preparation of supported on silica-gel benzene sulfonic acid: with chlorosulfonic acid (2.3 g; 0.020 mol) be dissolved in 10 mL carrene; The solution that forms under agitation dropwise adds and contains supported on silica-gel benzene (6.2 g; Immobilized benzene amount is 0.015 mol) 20 mL carrene suspension in, add continued and at room temperature stir 8 h; Mixture is filtered, and solid fully washs 3 times with carrene, then in vacuum drying chamber in 60 ℃ of dry 12 h down, obtain product 7.7 g.Through analyzing and calculating, the amount of supported on silica-gel benzene sulfonic acid is 2.27 mmol/g.IR?(KBr):?578,?852,?883,?1288,?2607?cm
-1。
The preparation of embodiment two, supported on silica-gel benzene sulfonic acid
The muriatic preparation of silica gel: take by weighing 10 g silochroms, place muffle furnace, behind 120 ℃ of drying 8 h, join in the reactor that reflux condensing tube and drying tube be housed; In container, add 20 mL thionyl chlorides, in 80 ℃ of 24 h that reflux, the color of system becomes yellow in the course of reaction, and As time goes on color is constantly deepened in the oil bath.After reaction finishes, filter, the gained solid product fully washs three times with carrene, remove desolvate the back in vacuum drying chamber in 60 ℃ of drying 10 h, obtain faint yellow solid product 10.5 g.Through analyzing and calculating, the supported quantity of Cl is 2.37 mmol/g in the silica gel chloride.
The preparation of supported on silica-gel benzene: with silica gel chloride (10.5 g, immobilized chlorine dose is 0.025 mol), phenol (4.0 g, 0.042 mol) joins in the carrene (40 mL), and 48 h then under agitation reflux; Filter, the gained solid fully washs 3 times with carrene, then in vacuum drying chamber in 60 ℃ of drying 12 h, obtain product 12.3 g.Through analyzing and calculating, the amount of supported on silica-gel benzene is 2.33 mmol/g.IR?(KBr):?680,?1103?cm
-1。
The preparation of supported on silica-gel benzene sulfonic acid: with chlorosulfonic acid (4.6 g; 0.040 mol) be dissolved in 20 mL carrene; The solution that forms under agitation dropwise adds and contains supported on silica-gel benzene (12.3 g; Immobilized benzene amount is 0.029 mol) 30 mL carrene suspension in, add continued and at room temperature stir 8 h; Mixture is filtered, and solid fully washs 3 times with carrene, then in vacuum drying chamber in 60 ℃ of dry 12 h down, obtain product 15.2 g.Through analyzing and calculating, the amount of supported on silica-gel benzene sulfonic acid is 2.31 mmol/g.IR?(KBr):?578,?852,?883,?1288,?2607?cm
-1。
The preparation of embodiment three, supported on silica-gel benzene sulfonic acid
The muriatic preparation of silica gel: take by weighing 15 g Kiselgel As, place muffle furnace, behind 120 ℃ of drying 8 h, join in the reactor that reflux condensing tube and drying tube be housed; In container, add 30 mL thionyl chlorides, in 80 ℃ of 24 h that reflux, the color of system becomes yellow in the course of reaction, and As time goes on color is constantly deepened in the oil bath.After reaction finishes, filter, the gained solid product fully washs three times with carrene, remove desolvate the back in vacuum drying chamber in 60 ℃ of drying 10 h, obtain faint yellow solid product 15.4 g.Through analyzing and calculating, the supported quantity of Cl is 2.24 mmol/g in the silica gel chloride.
The preparation of supported on silica-gel benzene: with silica gel chloride (15.4 g, immobilized chlorine dose is 0.034 mol), phenol (6.0 g, 0.063 mol) joins in the carrene (50 mL), and 48 h then under agitation reflux; Filter, the gained solid fully washs 3 times with carrene, then in vacuum drying chamber in 60 ℃ of drying 12 h, obtain product 18.1 g.Through analyzing and calculating, the amount of supported on silica-gel benzene is 2.21 mmol/g.IR?(KBr):?680,?1103?cm
-1。
The preparation of supported on silica-gel benzene sulfonic acid: with chlorosulfonic acid (6.9 g; 0.060 mol) be dissolved in 30 mL carrene; The solution that forms under agitation dropwise adds and contains supported on silica-gel benzene (18.1 g; Immobilized benzene amount is 0.040 mol) 60 mL carrene suspension in, add continued and at room temperature stir 8 h; Mixture is filtered, and solid fully washs 3 times with carrene, then in vacuum drying chamber in 60 ℃ of dry 12 h down, obtain product 22.8 g.Through analyzing and calculating, the amount of supported on silica-gel benzene sulfonic acid is 2.18 mmol/g.IR?(KBr):?578,?852,?883,?1288,?2607?cm
-1。
Embodiment four, supported on silica-gel benzene sulfonic acid catalysis Beckmann rearrangement
With 1; 2-dichloroethanes (4 mL) is added in the 50 mL flasks; Again with acetophenone oxime (0.14 g; 1 mmol) and embodiment one silica obtained immobilized benzene sulfonic acid (0.11 g; 0.25 mmol) add wherein respectively; Then flask is transferred in the micro-wave oven that reflux condensing tube and drying tube are housed, reaction is 5 minutes under the radiation of 455W microwave.After reaction finishes, filter, reclaim solid catalyst; With 1 in the filtrating, the 2-dichloroethanes is drained and is promptly got thick product, and thick product gets pure article---antifebrin behind column chromatography or recrystallization.Recording productive rate through gas-chromatography is 99%.
Antifebrin: m.p.:113.5-140 ℃.
1H NMR (400 MHz, CDCl
3): δ 2.11-2.17 (s, 3H, CH
3), 7.07-7.51 (m, 5H, Ar-H), 7.65 (s, 1H, NH). IR (KBr): 3293 (N-H), 1662 (C=O).
Embodiment five, supported on silica-gel benzene sulfonic acid catalysis Beckmann rearrangement
With 1; 2-dichloroethanes (4 mL) is added in the 50 mL flasks; Again with cyclohexanone oxime (0.11 g; 1 mmol) and embodiment two silica obtained immobilized benzene sulfonic acid (0.11 g; 0.25 mmol) add wherein respectively; Then flask is transferred in the micro-wave oven that reflux condensing tube and drying tube are housed, reaction is 6 minutes under the radiation of 455W microwave.After reaction finishes, filter, reclaim solid catalyst; With 1 in the filtrating, the 2-dichloroethanes is drained and is promptly got thick product, and thick product gets pure article---caprolactam behind column chromatography or recrystallization.Recording productive rate through gas-chromatography is 97%.
Caprolactam: m.p.:68-70 ℃.
1H NMR (400 MHz, CDCl
3): δ 1.62-1.79 (m, 6H, 3CH
2), 2.18-2.47 (t, 2H, COCH
2), 3.18-3.22 (t, 2H, NHCH
2), 7.03 (s, 1H, NH). IR (KBr): 3211 (N-H), 1660 (C=O).
Embodiment six, supported on silica-gel benzene sulfonic acid catalysis Beckmann rearrangement
With 1; 2-dichloroethanes (4 mL) is added in the 50mL flask; Again with diphenyl-ketoxime (0.20 g; 1 mmol) and embodiment three silica obtained immobilized benzene sulfonic acid (0.11 g; 0.25 mmol) add wherein respectively; Then flask is transferred in the micro-wave oven that reflux condensing tube and drying tube are housed, reaction is 6 minutes under the radiation of 455W microwave.After reaction finishes, filter, reclaim solid catalyst; With 1 in the filtrating, the 2-dichloroethanes is drained and is promptly got thick product, and thick product gets pure article---benzanilide behind column chromatography or recrystallization.Recording productive rate through gas-chromatography is 95%.
Benzanilide: 164.5 ℃ of m.p.:163 –.
1H NMR (400 MHz, CDCl
3): δ 7.13 – 7.87 (m, 10H, Ph-H), 7.90 (brs, 1H, NH). IR (KBr): 3344 (N – H), 1655 (C=O).
The Claisen rearangement of embodiment seven, pi-allyl aryl ether
With allyl phenyl ether (0.40 g; 3 mmol) and embodiment one silica obtained immobilized benzene sulfonic acid (0.22 g; The amount of immobilized benzene sulfonic acid is 0.5 mmol) in mortar, fully grind; Then it is transferred in the flask; The cover upper surface ware places microwave reactor to react 6 min (process of reaction is monitored by TLC) down in 650 W; After reaction finished, reactant mixture dissolved with 10 mL carrene, the filtered and recycled solid catalyst.Evaporate the dichloromethane solvent in the filtrating then, residue separates with ether recrystallization or with column chromatography (benzinum and ethyl acetate 8:1) and obtains the 2-chavicol, and productive rate is 96%.
2-chavicol: yellow liquid;
1H NMR (400 MHz, CDCl
3): δ 3.39 (d, 2H, J=4.8 Hz, CH
2), 5.09-5.15 (m, 2H, C=CH
2), 5.37 (s, 1H, OH), 5.95-6.06 (m, 1H, C=CH), 6.76-6.79 (m, 1H, ArH), 6.85-6.90 (m, 1H, ArH), 7.08-7.17 (m, 2H, ArH);
13C NMR (100 MHz, CDCl
3): δ 35.1,115.5, and 116.4,1210.7,125.3,127.4,130.5,136.3,154.2; IR (ν
Max/ cm
-1): 3434,3074,1592,1491,1232,753.
The Claisen rearangement of embodiment eight, pi-allyl aryl ether
With pi-allyl (3-aminomethyl phenyl) ether (0.44 g; 3 mmol) and embodiment two silica obtained immobilized benzene sulfonic acid (0.22 g; The amount of immobilized benzene sulfonic acid is 0.5 mmol) in mortar, fully grind; Then it is transferred in the flask; The cover upper surface ware places microwave reactor to react 7 min (process of reaction is monitored by TLC) down in 650 W; After reaction finished, reactant mixture dissolved with 10 mL carrene, the filtered and recycled solid catalyst.Evaporate the dichloromethane solvent in the filtrating then, residue separates with ether recrystallization or with column chromatography (benzinum and ethyl acetate 8:1) and obtains 2-pi-allyl-5-methylphenol, and productive rate is 94%.
2-pi-allyl-5-methylphenol: yellow liquid;
1H NMR (400 MHz, CDCl
3): δ 2.28 (s, 3H, CH
3), 3.36-3.43 (m, 2H, CH
2), 4.91-5.17 (m, 3H, OH and C=CH
2), 5.91-6.04 (m, 1H, C=CH), 6.64-6.78 (m, 2H, ArH), 6.97-7.03 (m, 1H, ArH);
13C NMR (100 MHz, CDCl
3): δ 19.6,30.5, and 113.2,116.0,122.2,123.9,127.1,136.4,138.3,153.7; IR (ν
Max/ cm
-1): 3441,2922,1635,1584,1467,1272,1111,778.
The foregoing description shows; The supported on silica-gel type benzene sulfonic acid catalyst of gained of the present invention has very high catalytic activity to two types of Atom economy reaction-Beckmann rearrangements and Claisen rearangement reaction; And catalyst is easily separated, can be recycled, and meets the national industrial policies of environmental protection.
Claims (8)
1. supported on silica-gel type benzene sulfonic acid Preparation of catalysts method comprises following processing step:
(1) the muriatic preparation of silica gel
The silica gel of drying is mixed with 1:2 ~ 1:4 weight ratio with thionyl chloride, in 75 ~ 85 ℃ of back flow reaction 20 ~ 24 h; Filter, the gained solid product fully washs with carrene, and vacuum drying obtains faint yellow silica gel chloride solids product;
(2) preparation of supported on silica-gel benzene product
Silica gel chloride and phenol are joined in the carrene stirring and refluxing 36 ~ 48 h with the weight ratio of 1:0.3 ~ 1:0.5; Filter, the gained solid product fully washs with carrene, and vacuum drying obtains supported on silica-gel benzene product;
(3) preparation of supported on silica-gel benzene sulfonic acid
The dichloromethane solution of chlorosulfonic acid is joined in the carrene suspension that contains supported on silica-gel benzene, at room temperature stir 4 ~ 8 h; The gained mixture filters, and solid fully washs with carrene, and vacuum drying obtains supported on silica-gel benzene sulfonic acid product; The weight ratio of said chlorosulfonic acid and supported on silica-gel benzene is 1:2 ~ 1:3.
2. supported on silica-gel type benzene sulfonic acid Preparation of catalysts method according to claim 1, it is characterized in that: said silica gel is macro porous silica gel, silochrom, Type B silica gel or Kiselgel A.
3. the product of method preparation is a supported on silica-gel type benzene sulfonic acid catalyst according to claim 1.
4. like the supported on silica-gel type benzene sulfonic acid catalyst of method preparation as described in the claim 3, it is characterized in that: the amount of supported on silica-gel benzene sulfonic acid is 2.18 ~ 2.31 mmol/g.
5. the supported on silica-gel type benzene sulfonic acid catalyst of method preparation is used for the Beckmann rearrangement of ketoxime according to claim 1.
6. be used for the Beckmann rearrangement of ketoxime like supported on silica-gel type benzene sulfonic acid catalyst as described in the claim 5, it is characterized in that: said ketoxime is acetoxime, 2-diacetylmonoxime, cyclopentanone oxime, cyclohexanone oxime, acetophenone oxime or diphenyl-ketoxime.
7. the supported on silica-gel type benzene sulfonic acid catalyst of method preparation is used for the Claisen rearangement reaction of pi-allyl aryl ether according to claim 1.
8. be used for the Claisen rearangement reaction of pi-allyl aryl ether like supported on silica-gel type benzene sulfonic acid catalyst as described in the claim 7, it is characterized in that: said pi-allyl aryl ether is allyl phenyl ether, pi-allyl p-tolyl ether, pi-allyl p-methoxyphenyl ether, pi-allyl rubigan ether, pi-allyl p-nitrophenyl ether, pi-allyl 1-naphthyl ether or pi-allyl 2-naphthyl ether.
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| CN105521823A (en) * | 2016-01-07 | 2016-04-27 | 哈尔滨理工大学 | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor |
| CN107694557A (en) * | 2017-10-23 | 2018-02-16 | 肇庆高新区国专科技有限公司 | A kind of macro porous silica gel loaded catalyst for acylation reaction |
| CN107721872A (en) * | 2017-10-18 | 2018-02-23 | 浙江农林大学 | A kind of method that ketoxime Beckmann rearrangement prepares acid amides |
| CN108117484A (en) * | 2017-12-15 | 2018-06-05 | 万华化学集团股份有限公司 | A kind of preparation method of citral |
| CN108620094A (en) * | 2017-03-21 | 2018-10-09 | 广州凌玮科技股份有限公司 | A kind of preparation method of four esterification catalyst sulfonation silica gel of carbon |
| CN111036298A (en) * | 2019-12-17 | 2020-04-21 | 华侨大学 | Preparation method and application of natural walnut shell powder sulfonic acid catalyst |
| CN114438072A (en) * | 2022-04-08 | 2022-05-06 | 山东天力药业有限公司 | Production method of trehalose |
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2011
- 2011-06-21 CN CN201110167042A patent/CN102302948A/en active Pending
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| PEYMAN SALEHI ET AL.: "Silica Sulfuric Acid and Silica Chloride as Efficient Reagents for Organic Reactions", 《CURRENT ORGANIC CHEMISTRY》 * |
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| CN105521823A (en) * | 2016-01-07 | 2016-04-27 | 哈尔滨理工大学 | Mesoporous-silica-gel surface bonded alkylsulfonic acid catalyst and preparation and catalysis methods therefor |
| CN108620094A (en) * | 2017-03-21 | 2018-10-09 | 广州凌玮科技股份有限公司 | A kind of preparation method of four esterification catalyst sulfonation silica gel of carbon |
| CN108620094B (en) * | 2017-03-21 | 2021-01-05 | 广州凌玮科技股份有限公司 | Preparation method of carbon tetra-esterification catalyst sulfonated silica gel |
| CN107721872A (en) * | 2017-10-18 | 2018-02-23 | 浙江农林大学 | A kind of method that ketoxime Beckmann rearrangement prepares acid amides |
| CN107694557A (en) * | 2017-10-23 | 2018-02-16 | 肇庆高新区国专科技有限公司 | A kind of macro porous silica gel loaded catalyst for acylation reaction |
| CN108117484A (en) * | 2017-12-15 | 2018-06-05 | 万华化学集团股份有限公司 | A kind of preparation method of citral |
| CN108117484B (en) * | 2017-12-15 | 2020-11-20 | 万华化学集团股份有限公司 | Preparation method of citral |
| CN111036298A (en) * | 2019-12-17 | 2020-04-21 | 华侨大学 | Preparation method and application of natural walnut shell powder sulfonic acid catalyst |
| CN114438072A (en) * | 2022-04-08 | 2022-05-06 | 山东天力药业有限公司 | Production method of trehalose |
| CN114438072B (en) * | 2022-04-08 | 2022-05-31 | 山东天力药业有限公司 | Production method of trehalose |
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