CN1094120C - Process for arylesterifying of phenol - Google Patents
Process for arylesterifying of phenol Download PDFInfo
- Publication number
- CN1094120C CN1094120C CN00134471A CN00134471A CN1094120C CN 1094120 C CN1094120 C CN 1094120C CN 00134471 A CN00134471 A CN 00134471A CN 00134471 A CN00134471 A CN 00134471A CN 1094120 C CN1094120 C CN 1094120C
- Authority
- CN
- China
- Prior art keywords
- phenol
- rare earth
- arylesterifying
- containing zeolite
- aromatic acid
- 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.)
- Expired - Fee Related
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method for the aromatic esterification of phenol. When a solvent or a dewatering agent exists, the hydroxybenzene is reacted with aromatic acid by heating or at refluxing temperature under the catalysis of rare earth molecular sieves to obtain ester. The present invention has the advantages of simple method, circular use for a rare earth catalyst and no environmental pollution.
Description
The present invention is a kind of aromatic esterization of rare earth containing zeolite catalysis phenol, obtains aromatic ester.
The spices of the ester class of phenol, food, pharmaceutical industries aspect are widely used, and also are the important source material of two arone compounds, and two arone are unusual useful as intermediates during UV UV stabilizer and medicine intermediate are produced.But because the conjugation of phenolic hydroxyl group and phenyl ring, the esterification of phenol is adopted three kinds of methods usually than Fatty Alcohol(C12-C14 and C12-C18) difficulty:
1, uses strong acylating agent, as acyl chlorides, acid anhydrides;
2, at OPCl
3, SOCl
2Halogenating agents etc. exist down, by acid and phenol direct esterification;
3, use some special couplers.First and two kind of method have the serious environmental pollution problem, and the third method is because the cost height only is suitable for the production of breadboard preparation or some specialty products.
The esterification of Fatty Alcohol(C12-C14 and C12-C18) can be used molecular sieve catalytic (Yang Jinzong, organic synthesis basis, Sinopec press, 1988).In the presence of beta-molecular sieve, Resorcinol can directly be reset with the aromatic acid reaction and be hydroxyl two arone compounds, but this method can only obtain the equilibrium mixture of ester and ketone, this has just limited the application [A.J.Hoefnagel of this method on producing, H.Van Bekkum, Appl.Catal.97 (1993) 87-102].So people are still at the process for arylesterifying of constantly exploring phenol.
The object of the invention provides a kind of process for arylesterifying of phenol.
The process for arylesterifying of phenol provided by the invention is to adopt rare earth containing zeolite as catalyzer, can represent with following formula:
Wherein Ar is an aryl, substituted aryl or thick aryl, and described substituted aryl is
, thick aryl is naphthyl, indenyl, anthryl, phenanthryl or Azulene base, R
1, R
2Or R
3=H, HO, C
nH
2n+1, C
nH
2n+1O or X, X=F, Cl, Br or I, n=1-8.
Used in the method for the invention rare earth containing zeolite can select suitable molecular sieve to make with conventional ion exchange method.Usually the rare earth oxide weight content is Re
2O
310-20% is comparatively suitable, and carrier can be used silicon oxide, aluminum oxide or above-mentioned two kinds of hopcalites.Commercially available Re-Y, Usery-A, Usery-B and Usy type rare earth catalyst all can be applicable to present method.During mixed carrier, SiO
2/ Al
2O
3Weight ratio be 1-10.As SiO in the Re-Y type rare earth containing zeolite
2/ Al
2O
3Weight ratio is 5.0, Re
2O
3～17%, contain NaO 2.0%, degree of crystallinity 95%, structure cell 24.6_.
In the method for the invention, the rare earth containing zeolite consumption is many, help reaction and carry out, the weight ratio of aromatic acid, rare earth containing zeolite and dewatering agent is 1 usually: 0.03-1: 0-0.1, but adopting the weight ratio of rare earth containing zeolite and aromatic acid is 0.05-0.20: the degree of 1 satisfaction that has reached.
Adopt method of the present invention, the mol ratio of phenol and aromatic acid is generally 1: 0.08-2, reaction is to carry out under heating or reflux temperature.Prolonging the reaction times also is favourable to finishing reaction, but in indivedual examples the long reaction times may cause the generation of rearrangement product hydroxyketone, the reaction times is 0.1-5h usually.
In the method for the invention, phenol and aromatic acid have water generates under rare earth containing zeolite catalysis.Carry out in order to add fast response, the method that can add dewatering agent with solvent azeotropic band water or in reaction is dewatered.
Dewatering with solvent azeotropic band water, usually can adopt aromatic hydrocarbons, halogenated aryl hydrocarbon, alkane, naphthenic hydrocarbon, hydrochloric ether as solvent, as benzene,toluene,xylene, chlorobenzene, dichlorobenzene, sherwood oil, normal hexane, normal heptane, hexanaphthene, ethylene dichloride, trichloroethane etc., can be according to temperature required selection of reaction.
Also can add dewatering agent in the method for the present invention and dewater, promptly in reacting by heating, add dewatering agent, as CaSO
4, CaCl
2, MgSO
4, dewatering agent such as molecular sieve.The mol ratio of aromatic acid and dewatering agent is 1: 0-10, and it also is favourable that more dewatering agent is finished reaction, the mol ratio of suggestion aromatic acid and dewatering agent is 1: 1-5.
Adopt method of the present invention, described phenol and aromatic acid generate ester under rare earth containing zeolite catalysis, can be in solvent the dehydration of azeotropic band water or add dewatering agent directly dehydration add fast response and carry out, do not have problem of environmental pollution, the catalyzer source is abundant, but market is buied, and the repeated use that can circulate, improve total conversion rate and can reclaim the back cover by raw material and be used for realizing, to some ester products of easily resetting, temperature controllable and time and prevent the generation of hydroxyketone.
The present invention will be helped to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1
In the there-necked flask that induction stirring, thermometer, water trap reflux condensing tube are housed, add P-hydroxybenzoic acid 19g, phenol 0.72g, commercially available SiO
2/ Al
2O
3Anharmonic ratio is 5.0, Re
2O
3～17%, NaO 2.0%, and degree of crystallinity is 95% Re-Y type rare earth containing zeolite 0.1-0.3g and dichlorobenzene 20ml, is heated to the about 20-30 of reflux water-dividing minute, stopped reaction, cooling is filtered, and washs with dichlorobenzene, merge mother liquor, desolventize, analyze with gas-chromatography GC, esterification yield is 70%.
Embodiment 2
With embodiment 1 operation, replacing rare earth containing zeolite with commercially available H-beta-molecular sieve is catalyzer, and it is 55% that GC analyzes esterification yield.
Embodiment 3
With embodiment 1, without the water trap dewatering, replace rare earth containing zeolite with dewatering agent, solubilizing agent does not add 1-5g CaSO
4Dehydration, it is 60% that GC analyzes esterification yield.After filtration, wash the recyclable rare earth containing zeolite of purifying.Purifying can obtain pure products.Solid adds entry 10-50ml, filters.
Embodiment 4
With embodiment 1, with different aromatic acid and the phenol reactants of commercially available Usy type rare earth containing zeolite catalysis, it is as follows that GC analyzes esterification yield:
Aromatic acid esterification yield (%)
Phenylformic acid 40
M-chlorobenzoic acid 10
Whitfield's ointment 45
Embodiment 5
With embodiment 1, with commercially available Usery-A type rare earth containing zeolite catalysis different phenol and anisic acid reaction, it is as follows that GC analyzes esterification yield:
Phenol esterification yield (%)
4-t-butyl phenol 67
Between-methylphenol 60
2,4 dichloro phenol 30
3,5-xylenol 50
4-octyl phenol 63
Embodiment 6
With embodiment 1, with different thick aryl phenols and to methoxybenzoic acid reaction, GC analysis esterification yield is as follows:
Thick aryl phenol esterification yield (%)
2-Naphthol 71
α-anthrol 68
Embodiment 7
With embodiment 1, between using-cresols and 4-hydroxy-benzoic acid or 4-octyl group benzoic acid, GC analyzes esterification yield and is respectively 57% and 45%.
Embodiment 8
With the rare earth containing zeolite of filtered and recycled among the embodiment 1, behind dichlorobenzene or acetone thorough washing, airing,, repeat the experiment of embodiment 1 at 450 ℃ of activation 2h, triplicate like this, GC analyzes esterification yield respectively, is followed successively by 69%, 72% and 71%.
Embodiment 9
The crude product that obtains among the embodiment 1, available recrystallization, ordinary method separated product and raw materials such as distillation or column chromatography.As crude product CH
2Cl
2The molten product P-hydroxybenzoic acid phenyl ester (m.p.174 ℃) that goes, remaining insolubles is phenol and P-hydroxybenzoic acid and a small amount of unsegregated ester, presses embodiment 1 esterification again, the secondary total conversion rate reaches 80%.
Claims (7)
1, a kind of process for arylesterifying of phenol is characterized in that molecular formula is that phenol, the molecular formula of ArOH is
Aromatic acid in the presence of rare earth containing zeolite, having or when solvent-free or dewatering agent, heating and reflux temperature be reaction 0.1-5h down, the mol ratio of phenol and aromatic acid is 1: 0.8-2.0, the weight ratio of aromatic acid, rare earth containing zeolite and dewatering agent is 1: 0.03-1: 0-0.1, wherein Ar is aryl, substituted aryl or thick aryl, and substituted aryl is
, thick aryl is naphthyl, indenyl, anthryl, phenanthryl or Azulene base, R
1, R
2Or R
3=H, HO, C
nH
2n+1, C
nH
2n+1O or X, X=F, Cl, Br or I, n=1-8, described rare earth containing zeolite contains rare earth Re
2O
310-20%, carrier are silicon oxide, aluminum oxide or its mixture.
2, the process for arylesterifying of phenol as claimed in claim 1 is characterized in that carrier S iO in the described rare earth containing zeolite
2/ Al
2O
3Weight ratio be 1-10.
3, the process for arylesterifying of phenol as claimed in claim 2 is characterized in that carrier S iO in the described rare earth containing zeolite
2/ Al
2O
3Weight ratio be 5, contain rare earth Re
2O
3～17%, contain NaO2.0%, degree of crystallinity 95%, structure cell 24.6_.
4, the process for arylesterifying of phenol as claimed in claim 1 is characterized in that azeotropic dehydration in the presence of solvent.
5, the process for arylesterifying of phenol as claimed in claim 1 or 2 is characterized in that described solvent is aromatic hydrocarbons, halogenated aryl hydrocarbon, alkane, naphthenic hydrocarbon or hydrochloric ether.
6, the process for arylesterifying of phenol as claimed in claim 1 is characterized in that described aromatic acid and dewatering agent mol ratio are 1: 1-5.
7, the process for arylesterifying of phenol as claimed in claim 1 is characterized in that described aromatic acid and rare earth weight ratio are 1: 0.05-0.20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00134471A CN1094120C (en) | 2000-02-25 | 2000-11-27 | Process for arylesterifying of phenol |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00111738.6 | 2000-02-25 | ||
| CN 00111738 CN1283609A (en) | 2000-02-25 | 2000-02-25 | Process for arylesterifying plenol |
| CN00134471A CN1094120C (en) | 2000-02-25 | 2000-11-27 | Process for arylesterifying of phenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1298864A CN1298864A (en) | 2001-06-13 |
| CN1094120C true CN1094120C (en) | 2002-11-13 |
Family
ID=25739365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN00134471A Expired - Fee Related CN1094120C (en) | 2000-02-25 | 2000-11-27 | Process for arylesterifying of phenol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1094120C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104611298B (en) * | 2015-01-31 | 2017-03-22 | 广东海大畜牧兽医研究院有限公司 | Cell affinity agent capable of improving duck flavivirus in-vitro infection efficiency and preparation method of cell affinity agent |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253131A (en) * | 1998-10-29 | 2000-05-17 | 宝山钢铁(集团)公司 | Process for preparing multiring or fused-ring binary carboxylate by heteropoly acid catalysis |
-
2000
- 2000-11-27 CN CN00134471A patent/CN1094120C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1253131A (en) * | 1998-10-29 | 2000-05-17 | 宝山钢铁(集团)公司 | Process for preparing multiring or fused-ring binary carboxylate by heteropoly acid catalysis |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1298864A (en) | 2001-06-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1194957C (en) | Process for the simultaneous coproduction and purification of ethyl acetate and isopropyl acetate | |
| US4605790A (en) | Phenol from coal and biomass | |
| CN1151108C (en) | Phenol recovery from BPA process waste streams | |
| CN1094120C (en) | Process for arylesterifying of phenol | |
| CN1084723C (en) | Process for preparing 5 -chloro-2, 3 -dihydro-1 H-inden -1 -one | |
| CN1283609A (en) | Process for arylesterifying plenol | |
| KR100852565B1 (en) | Hydrogenation of cleavage effluents in phenol production | |
| Firouzabadi et al. | Heteropoly acid cesium salt/cetyltrimethylammonium bromide a catalytic heterogeneous system which highly controls regioselective bromination of aromatic compounds with bromine | |
| CN1285819A (en) | Novel process for preparing ketimine | |
| CN101903320B (en) | Method for the production of 4,4'-[1-(trifluoromethyl)alkylidene]-bis-(2,6-diphenylphenols) | |
| US20090048470A1 (en) | Process for Producing Hydroxy Compound | |
| CN1213995C (en) | Method for the production of esters of unsaturated carboxylic acids | |
| US20050014982A1 (en) | Process for production of cumene | |
| CN114315530B (en) | Preparation process of m-tert-butylphenol and synthesis method of etoxazole | |
| Dumas et al. | The use of boron carbide powder as an efficient green catalyst for Friedel-Crafts chemistry. | |
| AU2006217965B2 (en) | Process | |
| US6979753B2 (en) | Process for preparation of 2-phenyl ethanol | |
| JP3881469B2 (en) | Alkenylphenols or isomer mixtures thereof | |
| CN100378044C (en) | Environment-friendly method for catalytic synthesis of naphthalene and indene derivatives by using montmorillonite | |
| Guisnet et al. | Molecular sieve catalysts as substitutes for metal chlorides in the chemical industry: Some selected examples | |
| CN1528724A (en) | Method for producing ethyl benzene | |
| JP5531312B2 (en) | Production method and use of polymer | |
| JP2024536036A (en) | Process for producing cresols and xylenes | |
| CN102219677A (en) | Method for producing oxalate by coupling carbon monoxide(CO) | |
| CN112299977A (en) | Method for preparing o-methoxyacetophenone by catalytic distillation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |