CN1234789A - Method of preparing trimethylbenzoquinone - Google Patents

Method of preparing trimethylbenzoquinone Download PDF

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CN1234789A
CN1234789A CN96180478A CN96180478A CN1234789A CN 1234789 A CN1234789 A CN 1234789A CN 96180478 A CN96180478 A CN 96180478A CN 96180478 A CN96180478 A CN 96180478A CN 1234789 A CN1234789 A CN 1234789A
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water
solvent
heteropolyacid
hpa
tmbq
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M－F·范德瓦勒
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Adisseo France SAS
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Rhone Poulenc Nutrition Animale SA
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    • 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
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Abstract

The invention concerns a novel method of preparing thimethyl hydroquinone (TMBQ) by oxidising trimethyphenol (TMP). It concers move particularly a method for oxidising trimethylphenol by a catalytic system consisting of heteropolyacids.

Description

The preparation method of Trimethylhydroquinone
The present invention relates to pseudocuminol (TMP) prepares Trimethylhydroquinone (TMHQ) through oxidation novel method.The present invention is more specifically to the method that adopts the catalyst system oxidation pseudocuminol that is made of heteropolyacid.
For a long time, for example according to the patent (EP127888 or EP167153) of gas chemical company of Mitsubishi, TMP has been oxidized to TMBQ has belonged to known content, the latter is the important intermediate of synthesising complex E.
According to above-mentioned patent, adopt oxygen-rich air oxidation TMP, adopt the mantoquita catalysis in gas phase/pure phase/water three-phase system to react.The TMP of molten state impouring continuously.Reaction terminating through decant, recycles the catalyzer that is in aqueous phase and is being in pure TMBQ in mutually through isolating after the different treatment.This method can obtain TMP transformation efficiency 100% and TMBQ yield 95%.
Figure A9618047800041
This method presents some defective, and catalyst system is dissolved in the organic phase by TMBQ and solvent composition particularly.Its regeneration need be with the acid treatment organic phase to reclaim catalyzer quantitatively.The type catalysis requires to use special material to avoid main corrosion because of using catalytic chlorinated derivatives to cause.
Can be by using extraordinary oxide catalyst (heteropolyacid catalyst) and using partition ratio to help catalyzer and regain the defective that overcomes this method with the round-robin solvent medium.
Heteropolyacid (HPA) is interpreted as the acid of heteropolyanion, and heteropolyanion is oxygenation anion, the heteroatoms X (X=B that contains 1 or 2 central atom 3+, Si 4+, Ge 4+, P 5+, As 5+) and the polyatom Y (Y=W, Mo, V) of 4 to 18 atoms of peripheral coordination.
Equally also a kind of of heteropolyanion or its salt can be included in the heteropolyacid.Solid-state HPA and salt thereof are made of heteropolyanion, counterion (hydrogen ion or metallic cation) and crystal water molecule.
Heteropolyanion has two kinds of primary structures:
The KEGGIN structural formula of heteropolyanion: X P+M 12O 40 (8-p)-
In the document the structure of frequent description be the KEGGIN structure, the ratio of the atoms metal/heteroatoms of this structure is 12/1.In this structure, be selected from atoms metal M in the VI family (M is preferably Mo or W) can be more or less for the atom of V family (M '=V, Co ...) replace.The X that is obtained P+M 12-nM ' nO 40 (8-p+n)-The HPA of type is above-mentioned mixture, is denoted as HPA-n.
The DAWSON structural formula of heteropolyanion: (X P+) 2M 18O 62 (16-2p)-
In this structure, the ratio of atoms metal/heteroatoms is 9/1.This structure is by two sections X that link to each other P+M 9O 34 (14-p)-Constitute.
About different HPA preparation methods, synthetic heteropolyanion generally forms via metal oxide and the oxygenation anion condensation that contains heteroatoms X in acidic medium.
For the mixed type heteropolyanion of synthetic KEGGIN structure, can use some synthetic method that can directly obtain the mixed type heteropolyanion of describing in the literature.
A) H 3+nPMo 12-nV nO 40The HPA-n of type, the wherein occasion of 1≤n≤6:
Three kinds of classical ways and novel recently electroosmose process have been described in the literature.
P.COURTIN, F.CHAUVEAU, P.SOUCHAY are at " academy of sciences's circular ", and 258 roll up, and 1964, the oldest method of describing in the 1247-1250 page or leaf can easily obtain the HPA-n of n≤3.This method is to dissolve the aqueous solution of cooling process Sodium orthomolybdate, sodium phosphate and vanadic acid sodium then through reflux again with the vitriol oil earlier.Extract the HPA-n that generates with ether from the aqueous solution, evaporating solvent is to obtain crystalloid HPA-n then.Yet yield is still on the low side, and when the n value raise, vanadate should be excessive greatly and be obtained a large amount of by products.
For example, according to patent JP77138499 embodiment, by molybdenum oxide (MoO 3) and vanadium oxide (V 2O 5) and phosphoric acid prepare H 5PMo 10V 2O 40The heteropolyacid of formula belongs to known content equally.Three kinds of reagent after reflux 20 days soluble in water, concentrated solution is to pure HPA-2 crystallization occurring then.
Same well-known, according to " kinetics and catalysis " such as ODYAKOV, 36 volumes, nineteen ninety-five, the 733-738 page or leaf is by H 3PO 4, MoO 3With ten vanadic acid H 6V 10O 28Formulations prepared from solutions HPA-n, wherein 1≤n≤6.According to the stoichiometry of desiring synthetic HPA-n, adjust the add-on of P, Mo and three kinds of reagent of V.By with vanadium oxide (V 2O 5) be dissolved in the cold water solution that contains 4 to 6% hydrogen peroxide and obtain ten vanadic acid solution.
For synthetic HPA-n, wherein n=1-4 little by little joins ebullient MoO with ten vanadic acid solution 3And H 3PO 4In the lean mixture.Keep stirring and seething with excitement until MoO 3Till dissolving fully, subsequent filtration.Reclaim filtrate, the i.e. aqueous solution of HPA-n.
For synthetic HPA-n, HPA-n ' (1≤n '≤4) solution replacement MoO use in n＞4 wherein 3Before adding ten vanadic acid solution lentamente with H 3PO 4Mix with HPA-n ' solution and seethe with excitement.Filter after the vaporize water.Filter residue is dissolved in 5% hydrogen peroxide solution and is added in the filtrate.
KHOZHEVNIKOV in nineteen ninety-five at " catalysis comment-scientific and engineering ", 37 volumes, propose the electrodialysis new synthetic method at nineteen ninety-five in the 311-352 page or leaf.HPA is created on anode, is water-soluble aqueous, and in the electrolysis of negative electrode generation water.Two electrodes separate with cationic exchange membrane, do not generate any by product.Yield reaches 100%.
HPA promptly can be used for homogeneous catalysis and also can be used for heterogeneous catalyst.They can be stated from silicon-dioxide, gac, the ion exchange resin.
About the main application scenario of HPA in the acid catalysis aspect, can enumerate condensation, hydration and dehydration, esterification and etherificate, nitrated, epoxidation, acetic acid decomposition, carbonylation, isomerization, oligomeric, phenol hydrocarbonylation, take off hydrocarbon and hydrocarbon shifts.
About oxidation, using maximum HPA is molybdovanaphosphoric acid, and its reason is its strong oxidation potential and good thermostability.The oxidizing reaction of HPA-n while catalyzing organic and inorganics.Therefore, but the oxygenant oxygen or the hydrogen peroxide of reaction.
The reduction-type of HPA is easy to reoxidize with oxygen.
It is that (production of maleic anhydride, cycloalkanes oxidation are the oxidation of pure and mild ketone, oxydehydrogenation, methane for the oxidation of alkane that redox catalysis is mainly used ...), alkene, alcohol (primary alconol, secondary alcohol ...), the oxidation and the inorganics (N of aldehyde 2H 4, NO, H 2S ...) oxidation.
Different authors considers to become with the system catalyzed oxidation TMP that contains HPA the possibility of TMBQ in homogeneous system water/acetate.Tested different types of HPA according to different operating method.
Be published in " Journal of Molecular Catalysis magazine " according to KHOLDEEVA etc., 75 volumes,, the article in the 235-244 page or leaf, TMP/HPA (H in 1992 as everyone knows like this 7PMo 8V 4O 40The KEGG1N structure) mol ratio is that 20 to obtain the TMBQ yield be 86%.
In addition, be published in " tetrahedron communication " according to SH1M1ZU etc. as everyone knows, 30 volumes, 1989, the article in the 471-474 page or leaf was at H 7PMo 12O 40The HPA of formula and hydrogen peroxide exist down can implement the process that TMP is oxidized to TMBQ.The TMBQ yield that is obtained reaches 78.3%.
R.NEUMANN is in " tetrahedron communication ", and 33 volumes 1992, are described the H that is used in the hexanol in the 1795-1798 page or leaf 5PV 2Mo 10O 40Under the 1 normal atmosphere oxygen in 60 ℃, TMP/HPA than being catalyzed oxidation 2,3 under 50 the condition, the 5-pseudocuminol becomes TMBQ, lasts 4 hours.Obtaining selectivity is 73%, and transformation efficiency is 75%.
Also there is article TMP to be oxidized to TMBQ in addition, can quotes JANSEN and the group member is published in " Journal of Molecular Catalysis magazine A chemistry ", 107 volumes,, the article in the 241-246 page or leaf in 1996 at this category with the HPA that is stated from the carbon.
Do not have one piece of article to describe and implement oxidation by catalyst recirculation mode easily.The present invention has realized this purpose.It relates in the presence of oxygenant that is selected from oxygen and hydrogen peroxide and heteropolyacid pseudocuminol and prepares the method for trimethylammonium oxygen quinone through oxidation, it is characterized in that this is reflected in the two phase liquid medium to carry out.
Pseudocuminol is preferably 2,3,6-pseudocuminol, the Trimethylhydroquinone that is obtained specifically 2,3,5-Trimethylhydroquinone.
Heteropolyacid is preferably from the heteropolyacid of KEGGIN structure or the heteropolyacid of DAWSON structure, and certainly, the salt of heteropolyacid is equally applicable in the scope of the invention.
Reaction medium is by water and contain 2 to 6 carbon atom unary organic carboxylic acids or binary organic carboxyl acid and water mixture that preferred acetate is formed constitutes.The volume ratio of organic acid and water is preferably between 95/5 and 20/80, more preferably between 80/20 and 60/40.
Choose from aliphatic hydrocrbon or aromatic hydrocarbons and from the also preferred chlorinated derivatives of their halide derivative with the solvent that the water unmixing also follows water to form two phase systems, more specifically preferably use orthodichlorobenzene.
Volume ratio between solvent and the aqueous systems (water and organic acid) is preferably between 30/70 and 90/10, more preferably between 30/70 and 50/50.
Mol ratio between pseudocuminol and the heteropolyacid preferably between 200/1 and 5/1, more preferably from about 10/1.
HPA and TMP together and the weight ratio between the liquid medium of forming by solvent and water medium preferably between 0.1% and 15%, more preferably from about 6%.
About reaction conditions, service temperature preferably is higher than 30 ℃, more preferably between 50 and 70 ℃.Oxygen pressure is preferably between 0.2 and 1 crust.
According to implementing optimal way of the present invention, after the reaction, the decant reaction medium will be so that will contain the water and the separated from solvent that contains TMBQ of HPA.Then, organic phase is through dehydration, and solvent is through distillation, and circulation subsequently is used for new oxidation step, distillation TMBQ.Water is determined on a case-by-case basis and handles to remove dissolved TMBQ with orthodichlorobenzene, looked particular case then and concentrated before being circulated to oxidation step.
Present method need not any brackish water treating processes, does not generate the inorganic salt that any need are abandoned, the whole circulation of employed solvent, and the TMBQ product purity is very high.Owing to the etching problem of above-mentioned chlorination catalyst do not occur, the opinion with employed reactant character, the chosen process of compatible material obtain simplifying.
The following examples are described more comprehensively to the present invention.
Embodiment
I) preparation of heteropolyacid
According to " kinetics and catalysis " such as ODYAKOV, 36 volumes, nineteen ninety-five, the method that the 733-738 page or leaf is described prepares H 7PMo 8V 4O 40
II) TMP is oxidized into the process of TMBQ.
Some test is implemented with intermittent mode, reacts initial moment adding total overall reaction thing; Other tests are implemented with semi-batch mode, add the TMP that treats oxidation continuously.
A) install
Be reflected to be equipped with in water cooler, sintered filter and the churned mechanically 250 milliliters of four-hole bottles and implement.Reaction medium heats by thermostatic bath.The oxygen pressure that forms above reaction medium by feeding pure oxygen in reactor is 1 normal atmosphere.Under meter can be regulated the flow of oxygen.
In semibatch test occasion, the TMP that is dissolved in organic solvent dropwise joins in the reaction medium by syringe and propelling syringe.It is adjustable advancing the syringe fltting speed, so can decide dripping to tachy sterol.
B) operating method
Total Test in 50 ℃ of thermostatic baths, oxygen flow is to implement under 12 liters of/hour conditions.
The intermittent type test
Add 3 gram molten states in the reactor, i.e. TMP after baking oven internal heating to 70 ℃.Add 15 milliliters of HPA (H again 7PMo 8V 4O 40) aqueous solution (0.15 mol) and 55 milliliters of acetate 50 milliliters of orthodichlorobenzenes then.
Start and stir and aerating oxygen.Put reaction medium in 50 ℃ of water-baths.
React after 2 hours, topple over reaction mixture in separating funnel, and wash reactors with 30 milliliters of orthodichlorobenzenes.Be dissolved in TMBQ in the relict catalyst with twice of the water of 30 milliliters of orthodichlorobenzene washing and recycling with extraction, reclaim all phases, and two alternate each are weighed and measurement volumes mutually.
The semibatch test
Implement aforesaid method, wherein do following change:
3g TMP is dissolved in 50 milliliters of organic solvents and stirring and oxygen is depressed by syringe and advance syringe to add this solution in 1 and a half hours, feed in raw material and left standstill 30 minutes after finishing.
The recycling of TMBQ and relict catalyst is identical with interrupter method.
C) result
Water and organic two-phase are analyzed with high pressure lipuid chromatography (HPLC) (CLHP).
The transformation efficiency of TMP is TT=100%, and the TMBQ yield is RR=84% in the TMBQ amount of the TMP acquisition that adds promptly.Major impurity is well-known hexamethyl biphenol (HMDP) and undeterminate heavy constituent as byproduct of reaction.The result of intermittent type and semibatch obviously is identical.
The most interesting result is that catalyzer is present in aqueous phase quantitatively, need not to handle in addition to be recycled with its original form.
III) research of catalyst system recyclability
The recyclability test
At two best phase systems of performance, promptly in orthodichlorobenzene/acetic acid/water=50 milliliter/56 milliliters/14 mL media, carry out the research of catalyst system recyclability, study with the intermittent type test.
A) install
The used installation of round-robin test is identical with the installation of multiphase medium batch test.
B) operating method
The water that contains catalyzer that is obtained when rotatory evaporator evaporates first catalytic cycle termination of describing at last paragraph is added 56 milliliters of acetate then until obtaining black slightly oil, adds 14 ml waters again.
In reactor, add molten state, i.e. TMP after baking oven internal heating to 70 ℃ (3 gram).Add above-mentioned catalytic solution and add 50 milliliters of orthodichlorobenzenes again.
Later step is identical with first catalytic cycle.
C) result
Come into effect three circulations from same catalyst system.Under same operational condition, implement oxidation each time.
Used HPA:H 7PMo 8V 4O 40
T=50℃
P=1 normal atmosphere oxygen
TMP mole number/HPA mole number=10
The medium of organic solvent/acetic acid/water is formed: 50 milliliters/56 milliliters/14 milliliters
The reaction last=2 hours
TT％ Selectivity % TMBQ yield % HMDP yield %
First catalytic cycle 100 ????84 ????84 ????0.2
Second catalytic cycle 100 ????86 ????86 ????1
The 3rd catalytic cycle 100 ????85 ????85 ????2
The catalyst system activity does not reduce between each circulation.

Claims (12)

1. in the presence of the oxygenant of selecting from oxygen and hydrogen peroxide and heteropolyacid 2,3, the 6-pseudocuminol is through oxidation preparation 2,3, and the method for 5-Trimethylhydroquinone is characterized in that this is reflected in the two phase liquid medium to implement.
2. according to the method for claim 1, it is characterized in that heteropolyacid selects from the heteropolyacid of the heteropolyacid of KEGGIN structure or DAWSON structure.
3. according to the method for claim 1, it is characterized in that reaction medium is by water and C 2To C 6Type unary organic carboxylic acid or binary organic carboxyl acid and the aqueous mixture formation of being formed with the immiscible organic solvent of water.
4. according to the method for claim 3, it is characterized in that volume ratio between acetate and the water is between 95/5 and 20/80, preferably between 80/20 and 60/40.
5. according to the method for claim 3, it is characterized in that from aliphatic hydrocrbon or aromatic hydrocarbons and from their halide derivative, choosing with the immiscible solvent of water.
6. according to the method for claim 5, it is characterized in that with the immiscible solvent of water be orthodichlorobenzene.
7. according to the method for claim 3, it is characterized in that volume ratio between solvent and the Aquo System is between 30/70 and 90/10 and preferably between 30/70 and 50/50.
8. according to the method for claim 1, it is characterized in that mol ratio between pseudocuminol and the heteropolyacid is between 200/1 and 5/1 and preferred about 10/1.
9. according to the method for claim 1, it is characterized in that HPA and TMP together and the weight ratio between the liquid medium of forming by solvent and water-bearing media between 0.1% and 15% and preferred about 6%.
10. according to the method for claim 1, it is characterized in that temperature of reaction is higher than 30 ℃, and preferably between 50 and 70 ℃.
11., it is characterized in that oxygen pressure is between 0.2 and 1 crust according to the method for claim 1.
12. method according to claim 1, decant reaction medium after it is characterized in that reacting will be so that will contain the water and the separated from solvent that contains TMBQ of HPA, then, organic phase is through dehydration, solvent is used for the new step of oxidation through distillation and circulation, distillation TMBQ, water is looked particular case and is concentrated and be circulated to oxidation step with the orthodichlorobenzene processing then to remove dissolved TMBQ.
CN96180478A 1996-10-28 1996-10-28 Method of preparing trimethylbenzoquinone Pending CN1234789A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787860A (en) * 2014-01-27 2014-05-14 安徽丰原发酵技术工程研究有限公司 Preparation method of 2,3,5-trimethylbenzoquinone
CN114717571A (en) * 2022-03-30 2022-07-08 东北师范大学 Anolyte and benzaldehyde and hydrogen coupling co-production system and application

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103787860A (en) * 2014-01-27 2014-05-14 安徽丰原发酵技术工程研究有限公司 Preparation method of 2,3,5-trimethylbenzoquinone
CN114717571A (en) * 2022-03-30 2022-07-08 东北师范大学 Anolyte and benzaldehyde and hydrogen coupling co-production system and application
CN114717571B (en) * 2022-03-30 2023-11-24 东北师范大学 Anolyte and benzaldehyde and hydrogen coupling co-production system and application

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