CN103508838B - Preparation method of diphenylmethane compounds - Google Patents
Preparation method of diphenylmethane compounds Download PDFInfo
- Publication number
- CN103508838B CN103508838B CN201210224039.2A CN201210224039A CN103508838B CN 103508838 B CN103508838 B CN 103508838B CN 201210224039 A CN201210224039 A CN 201210224039A CN 103508838 B CN103508838 B CN 103508838B
- Authority
- CN
- China
- Prior art keywords
- catalyzer
- phenylcarbinol
- reaction
- accordance
- benzene
- 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
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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- 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)
- Catalysts (AREA)
Abstract
The invention relates to a preparation method of diphenylmethane compounds. The structural formula of the prepared diphenylmethane compounds is shown in the specification, wherein R1 and R2 are ortho-position, meta-position or para-position substituent groups, and can be groups such as -H, -CH3, -OCH3, -CH2CH3, -CH(CH3)2, -C(=O)CH3, -F, -Cl, -CF3 and the like. The preparation route comprises the following steps: adding benzene or derivatives thereof, benzyl alcohol or chlorobenzyl alcohol or derivatives thereof and a catalyst into a reaction vessel; after reaction, separating out the catalyst; and distilling to separate, thus obtaining the diphenylmethane compounds, wherein the catalyst is composite oxide composed of Mo, Nb, W, V and the like; the conversion rate of the reaction materials is 100% (measured by benzyl alcohol or chlorobenzyl alcohol or derivatives thereof); the separation yield of the diphenylmethane compounds is up to 90% or above; and the catalyst can be recycled repeatedly with the activity and selectivity unchanged.
Description
Technical field
The invention belongs to organic synthesis field, be specifically related to the preparation method of ditane compounds.
Background technology
Carbon carbon (C-C) linked reaction is important methodology of organic synthesis, is mainly used in synthesis of natural product, medicine, agricultural chemicals and functional materials etc.Fu's one gram of alkylated reaction is a class widely used carbon carbon (C-C) linked reaction.Generally under the catalysis that strong Lewis is sour or Bronsted is sour, halohydrocarbon is used to carry out alkylation to an aromatic ring.But these catalyzer are difficult to reclaim after the reaction, can not reuse.Therefore the high reactivity that can recycle is developed and high-selectivity catalyst can make this route have more industrial application value.
Ditane compounds is mainly used in perfume industry, is the important intermediate of organic synthesis.Medicine industry is mainly used in the production of diphenhydramine hydrochloride.Ditane can be used for preparing essence and perfume etc.Its derivative also can be used as the synthesis of the drug molecules such as belarizine, CN, oxatomide.
Ditane compounds industrially adopts the liquid catalyst such as sulfuric acid, hydrofluoric acid or the homogeneous phase such as aluminum chloride, zinc chloride Lewis acid catalyst.These catalyzer operational difficultys, equipment corrosion is serious, and aftertreatment produces a large amount of waste water and waste residue, and catalyzer can not be reused.Lewis acid is loaded on the carrier such as silicon oxide, aluminum oxide, the solid catalyst being insoluble in water can be prepared.CN102329191A discloses a kind of catalyzer of immobilized aluminum chloride, and the yield preparing ditane is 93%.US2927087 and US3449264 discloses the catalyzer of immobilized aluminum chloride.But because aluminum chloride and water electrode easily react, catalyst activity component runs off serious, and the aluminum chloride after running off increases the corrosion of conversion unit, strengthens with the separating difficulty of product.Crystalline oxide has very high hydrothermal stability, generally needs load active component just to can be used as catalyzer and uses, adopt the report of the metal oxide catalyst of pure phase less.Document (Chemistry-A European Journal 15 (3): 742-753) and patent JP2009067753 disclose the preparation of molybdenum trioxide catalyst for ditane compounds, the method catalyst preparing is simple, but the specific surface area of catalyzer is little, shaping of catalyst difficulty, and adopt pure molybdenum trioxide catalyst, catalyzer cost is higher, is not suitable for large-scale production and application.For reactant molecule phenyl ring having electron-withdrawing substituent as ethanoyl, trifluoromethyl etc., the yield of ditane compounds is lower than 20%.Document (Catalysis Today 144 (3-4): 358-361) reports the application of a kind of Mo-V-O catalyzer in catalyzed reaction.This catalyzer is the crystalline oxide of compound, has orderly pore passage structure, high-specific surface area and Surface Oxygen room as Lewis acidic site, and the potential an acidic catalyst that can be used as uses.
Exploitation has acid complex metal oxides porous catalyst, and realize the preparation of ditane compounds under mild conditions, be the production method that people expect always.
Summary of the invention
Preparation method that the object of this invention is to provide a kind of low cost, that be better than resultful ditane compounds at present.Briefly adopt M (Mo, Nb, W)-V-O catalyzer, there is C-C linked reaction (Benzylation reaction) in catalysis benzene or benzene derivate and phenylcarbinol or chlorobenzyl alcohol or their derivative under liquid-phase condition, generates ditane compounds.
Adopt present method can prepare the ditane compounds with following structure.
R
1and R
2for the substituting group of ortho position, a position or contraposition, can be-H ,-CH
3,-OCH
3,-CH
2cH
3,-CH (CH
3)
2,-C (=O) CH
3,-F ,-Cl ,-CF
3deng group.Its synthetic route is as follows:
In reaction vessel, add the one in benzene or substituted benzene, substituted benzene is with following substituting group-CH on phenyl ring
3,-OCH
3,-CH
2cH
3,-CH (CH
3)
2,-C (=O) CH
3,-F ,-Cl ,-CF
3in a kind of benzene derivate; Add with substituent compound on phenylcarbinol, chlorobenzyl alcohol or their benzene ring structure, substituting group is-CH again
3,-OCH
3,-CH
2cH
3,-CH (CH
3)
2,-C (=O) CH
3,-F ,-Cl ,-CF
3in one; And catalyzer, isolate catalyzer after reaction, go out ditane compounds through fractionation by distillation.The Main By product that reaction generates is water or hydrogenchloride.This reaction for solvent with benzene or benzene derivate, adopts reflux or passes into the elementary operations such as rare gas element, except anhydrating and hydrogenchloride, making to react the generation direction be conducive to ditane and carrying out.At ambient pressure, increasing pressure does not have obvious promoter action to this reaction in this reaction.Temperature of reaction has catalytic result to have remarkably influenced.Generally carry out near the boiling point of benzene or benzene derivate, adopt the method for reflux.But temperature of reaction is not higher than 150 DEG C, be preferably 50-150 DEG C.Temperature of reaction is too high, the side reaction of more difficult generation on thermodynamics increases (reaction such as side chain alkylation, etherificate, dehydrogenation), reduce the selectivity of ditane compounds, and at relatively high temperatures, the effect in organic molecule and water molecules or hydrogenchloride and active centre increases, destroy active structure, stability reduces, and can be used repeatedly degradation.Although in experimentation, experiment blast never occurs and waits hazard event, benzene or benzene derivate at high temperature, have the danger of blasting, and therefore need the strict control to temperature of reaction.According to the difference of reactant, charging capacity, temperature of reaction etc., can suitably increase and Reaction time shorten, find through investigating, the reaction times was advisable in 5-360 minute, and selectivity of product is higher, and preferably the reaction times is at 10-30 minute.
The concentration of phenylcarbinol or chlorobenzyl alcohol or their derivative has remarkably influenced to reaction, due to the compound that reaction product is containing benzene ring structure, if it is higher that it generates concentration, the probability continuing to occur side reaction is larger, therefore strictly should control the concentration of phenylcarbinol or chlorobenzyl alcohol or their derivative in the reaction, object controls the generation concentration of product in reaction system.The volumetric concentration of phenylcarbinol or chlorobenzyl alcohol or their derivative is 1-60%, and preferably volumetric concentration is 5-10%.This reaction is the reaction of kinetic control, increase the usage quantity of catalyzer and significantly can increase benzene or the Benzylation speed of reaction of benzene derivate, but too high catalyst concn, add cost, the mass-transfer efficiency of reaction system reduces and product molecule continues Benzylation probability increase, and selectivity of product declines on the contrary.The effects finds, the 1-30% that the operating weight of catalyzer accounts for reaction mixture gross weight is suitable, and preferably operating weight is 3-10%.The solid catalyst that present method adopts, can isolate catalyzer by methods such as centrifugation, suction filtration or press filtrations after reaction.After adopting underpressure distillation to isolate solvent, can obtain the crude product of ditane compounds, continuing purifying can obtain sterling.Reaction raw materials transformation efficiency 100% (in phenylcarbinol or chlorobenzyl alcohol or their derivative), the separation yield more than 90% of ditane compounds.M (Mo, Nb, W)-V-O catalyzer has reusable clear superiority repeatedly.After catalyst separating, through simple solvent wash, dry after, can Reusability more than 1 time, and the state of catalyzer and catalytic activity thereof and selectivity do not change.
Catalyzer prepared by the present invention has M (Mo, Nb, W)-V-O structure.Mo-V-O catalyzer (001) direction, edge preferential growth in preparation process is nano bar-shape structure.Research finds that the active crystal face of catalyzer is that { 001} basal plane is exposed to the crystal face at nano bar-shape two ends.Its catalytic active center is the tetrahedron of Mo and octahedra 7 Yuans rings combining with the tetrahedron of V and 6 Yuans ring structures, and opening diameter is 0.4 nanometer.By the tetrahedron of Mo or the octahedra method adopting isomorphous substitution, prepare containing heteroatomic Mo-V-O structure, more acid sites can be introduced.Existing research shows, isomorphous substitution is the effective means building surface acidity center, because not homoatomic coordination environment there are differences, and adjacent atom and oxygen form tetrahedron or octahedra time, be the reason producing acid sites with the difference of the coordination ability at oxygen center.The preparation process of catalyzer be by the presoma of Mo, Nb, W etc. and V according to after certain mol proportion example fully ground and mixed, more than 300 DEG C, make this catalyzer after thermolysis.Decomposition reaction is there is and generates oxide structure in most metals presoma more than 300 DEG C.But the temperature of thermolysis can not higher than the fusing point of metal oxide or sublimation temperature point.Too high decomposition temperature makes oxide compound generation crystal transition, hinders the growth of pore structure and the generation of crystal.General heat decomposition temperature controls between 300 DEG C-600 DEG C.Thermal decomposition process forms the tetrahedron of M (Mo, Nb, W) and necessary condition that is octahedra and the tetrahedron formation rule ring texture of V.Suitable thermolysis atmosphere is conducive to the quantity and the structure that control to show Lacking oxygen.At the atmosphere heatable catalyst of oxygen deprivation, ambient oxygen partial pressure is lower, and Sauerstoffatom tends to depart from oxide surface, generates Lacking oxygen.Low temperature and high density oxygen-containing atmosphere are all unfavorable for forming Lacking oxygen.Find in an experiment, in thermolysis atmosphere, the volume ratio of oxygen is 0 to 21%, and remaining gas can be the rare gas elementes such as helium, nitrogen, argon gas, and preferably ratio is 0 to 5%.The present invention to the selection of metal precursor based on this presoma under 300-600 DEG C of thermolysis condition, can form oxide compound is principle, and preferably the presoma of Mo, Nb, W and V is for being ammonium molybdate, potassium molybdate, Sodium orthomolybdate, molybdenum oxide, molybdenum chloride, niobium oxides, columbium pentachloride, ammonium niobium oxalate, wolframic acid, tungsten hexacarbonyl, ammonium tungstate, Tungsten oxide 99.999, ammonium meta-vanadate, vanadylic sulfate, vanadium acetylacetonate and vanadyl chloride etc.
In catalyzer, the molar ratio of each component will strictly control.The prerequisite forming pore structure and 7 Yuans rings and 6 Yuans ring structures is that the octahedral and tetrahedral of M appropriately mates with the tetrahedron of V.The ratio of single-element is too high can form dephasign structure, reduces catalytic performance.Study tour finds that (Mo+Nb+W)/V molar ratio is that 1-6 is more suitable to M, and better condition is 2-4, and top condition is 3.The ionic radius of Mo, Nb and W is respectively Mo
6+62pm, Nb
5+70pm and W
6+62pm, ionic radius size is close, is easy to that isomorphous substitution occurs and forms the tetrahedron of hetero atom structures and octahedra clustering architecture.The molar ratio of any one amount of substance wherein between Mo, Nb, W and the amount of substance of whole Mo, Nb, W is for being not less than 0.1.
In sum, the present invention is by regulation and control preparation condition, obtain the solid heterogeneous catalyst with M (Mo, Nb, W)-V-O structure, with benzene or benzene derivate, phenylcarbinol or chlorobenzyl alcohol or their derivative etc. in the C-C coupling reaction of reactant, show higher catalytic performance and repeat performance.Reaction raw materials transformation efficiency 100% (in phenylcarbinol or chlorobenzyl alcohol or their derivative), the separation yield more than 90% of ditane compounds.After catalyst separating, through simple solvent wash, dry after, can Reusability more than 1 time, and the state of catalyzer and catalytic activity thereof and selectivity do not change.The method route of this invention overcomes the shortcoming of homogeneous catalyst and load method Kaolinite Preparation of Catalyst, has the advantages such as reaction conditions gentleness, technique are simple, processing ease, is suitable for large-scale production ditane compounds.
Embodiment
Embodiment 1
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80] and 5.04g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 5%O
2/ N
2mixed gas, with 10 DEG C of min
-1speed be warming up to 400 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 2.0g prepared, benzene 50mL and phenylcarbinol 2.5mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 100%, and ditane selectivity is more than 99%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 92%.
Embodiment 2
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80] and 2.52g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 0%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 500 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 3.0g prepared, benzene 60mL and phenylcarbinol 3.5mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 10 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 95%, and ditane selectivity is 96%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 88%.
Embodiment 3
By 10.00g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3] and 3.40g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 10%O
2/ He mixed gas, with 10 DEG C of min
-1speed be warming up to 600 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 2.0g prepared, benzene 4mL and phenylcarbinol 4.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 60 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 90%, and ditane selectivity is 95%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 83%.
Embodiment 4
By 10.00g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) and 2.77g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 21%O
2/ N
2mixed gas, with 10 DEG C of min
-1speed be warming up to 450 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 2.0g prepared, benzene 4mL and phenylcarbinol 4.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 30 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 98%, and ditane selectivity is 95%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 80%.
Embodiment 5
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 3.02g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 5.93g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3] and put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 5%O
2/ N
2mixed gas, with 10 DEG C of min
-1speed be warming up to 450 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 2.0g prepared, benzene 50mL and phenylcarbinol 2.5mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 20 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 100%, and ditane selectivity is more than 95%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 85%.
Embodiment 6
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 3.02g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 9.11g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 10%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 650 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 3.0g prepared, benzene 50mL and phenylcarbinol 5.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 90%, and ditane selectivity is more than 95%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 79%.
Embodiment 7
By 10.00g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3], 2.51g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 3.51g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 15%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 350 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 3.0g prepared, benzene 50mL and phenylcarbinol 5.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 5 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 95%, and ditane selectivity is more than 96%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 81%.
Embodiment 8
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 14.82g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3], 15.12g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 18.22g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 21%O
2/ He mixed gas, with 10 DEG C of min
-1speed be warming up to 500 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 3.0g prepared, benzene 40mL and phenylcarbinol 8.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 30 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 97%, and ditane selectivity is more than 98%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 90%.
Embodiment 9
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 4.94g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3], 7.56g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 6.07g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 10%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 500 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 3.0g prepared, benzene 60mL and phenylcarbinol 8.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 45 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 93%, and ditane selectivity is more than 95%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 88%.
Embodiment 10
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 2.96g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3] and 6.05g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 17%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 550 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 2.0g prepared, benzene 60mL and phenylcarbinol 8.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 15 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 90%, and ditane selectivity is more than 90%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 73%.
Embodiment 11
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80] and 6.07g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 3%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 600 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order particle.
Get above-mentioned the catalyzer 1.0g prepared, benzene 60mL and phenylcarbinol 4.0mL and put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 97%, and ditane selectivity is more than 97%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 91%.
Embodiment 12
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80] and 4.00g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 5%O
2/ N
2mixed gas, with 10 DEG C of min
-1speed be warming up to 450 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order size particles.
Get above-mentioned the catalyzer 2.0g prepared, toluene 40mL and phenylcarbinol 1.0mL and put into reaction vessel, connect reflux, put into the oil bath (115 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 97%, and mixing (between neighbour to) methyidiphenylmethane selectivity is more than 99%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating mixing ditane is 90%.
Embodiment 13
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 4.94g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3], 4.56g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 6.07g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 7%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 300 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order size particles.
Get above-mentioned the catalyzer 1.0g prepared, p-Xylol 40mL and phenylcarbinol 2.0mL and put into reaction vessel, connect reflux, put into the oil bath (145 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is the selectivity of 100%, 2-benzyl-Isosorbide-5-Nitrae-p-Xylol is more than 96%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating 2-benzyl-Isosorbide-5-Nitrae-p-Xylol is 90%.
Embodiment 14
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 5.94g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3], 1.56g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 6.07g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 7%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 300 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order size particles.
Get above-mentioned the catalyzer 2.0g prepared, sym-trimethylbenzene 70mL and phenylcarbinol 1.0mL and put into reaction vessel, connect reflux, put into the oil bath (150 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 50 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is the selectivity of 94%, 2-benzyl-1,3,5-sym-trimethylbenzene is more than 90%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating 2-benzyl-1,3,5-sym-trimethylbenzene is 75%.
Embodiment 15
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80] and 5.04g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 5%O
2/ N
2mixed gas, with 10 DEG C of min
-1speed be warming up to 400 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order size particles.
Get above-mentioned the catalyzer 2.0g prepared, sym-trimethylbenzene 70mL and phenylcarbinol 1.0mL and put into reaction vessel, connect reflux, put into the oil bath (150 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is the selectivity of 94%, 2-benzyl-1,3,5-sym-trimethylbenzene is more than 90%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating 2-benzyl-1,3,5-sym-trimethylbenzene is 75%.
Embodiment 16
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 0.96g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3] and 3.05g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 10%O
2/ Ar mixed gas, with 10 DEG C of min
-1speed be warming up to 500 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order size particles.
Get above-mentioned the catalyzer 1.0g prepared, ethylbenzene 70mL and phenylcarbinol 3.0mL and put into reaction vessel, connect reflux, put into the oil bath (145 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 30 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 100%, and the selectivity of mixing (between neighbour to) ethyl ditane is more than 95%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating 2-benzyl-1,3,5-sym-trimethylbenzene is 86%.
Embodiment 17
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 2.98g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3], 10.27g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 7.34g niobic acid ammonium oxalate hydrate (C
4h
4nNbO
9xH
2o, molecular weight 302.98) put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 21%O
2/ N
2mixed gas, with 10 DEG C of min
-1speed be warming up to 560 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order size particles.
Get above-mentioned the catalyzer 3.0g prepared, isopropyl benzene 100mL and phenylcarbinol 5.0mL and put into reaction vessel, connect reflux, put into the oil bath (150 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 20 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is the selectivity of 96%, 2-benzyl isopropyl benzene is more than 98%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 89%.
Embodiment 18
Adopt the catalyzer of embodiment 1, catalyzer 2.0g, methyl phenyl ketone 50mL and phenylcarbinol 4.5mL put into reaction vessel, connect reflux, put into the oil bath (150 DEG C) of preheating, start to stir, start timing when occurring Deng backflow phenomenon, react after 60 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 100%, and the selectivity of mixing (between neighbour to) benzyl methyl phenyl ketone is more than 95%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating mixing (between neighbour to) benzyl methyl phenyl ketone is 85%.
Embodiment 19
Adopt the catalyzer of embodiment 7, catalyzer 2.0g, fluorobenzene 100mL and phenylcarbinol 1.5mL put into reaction vessel, connect reflux, put into the oil bath (90 DEG C) of preheating, start to stir, start timing when occurring Deng backflow phenomenon, react after 60 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 100%, is more than 90% to the selectivity of benzyl fluorobenzene.Through suction filtration by catalyst separating, filtrate decompression distilled, isolating the crude yield of benzyl fluorobenzene is 83%.
Embodiment 20
Adopt the catalyzer of embodiment 6.Catalyzer 2.0g, fluorobenzene 100mL and phenylcarbinol 1.5mL put into reaction vessel, connect reflux, stop after 60 minutes, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 100%, is more than 80% to the selectivity of benzyl phenylfluoroform.Through suction filtration by catalyst separating, filtrate decompression distilled, isolating the crude yield of benzyl fluorobenzene is 72%.
Embodiment 21
By 10.00g Ammonium Heptamolybdate [(NH
4) Mo
7o
244H
2o, molecular weight 1163.80], 7.01g vanadylic sulfate (VOSO
4nH
2o, 64.83% Vanadosulfuric acid weight content) and 2.73g ammonium metawolframate [((NH
4)
6h
2w
12o
40, molecular weight 2956.3] and put into mortar, add after 15mL water fully grinds 10 minutes, put into 110 DEG C of baking ovens, pass into dry air 12 hours, take out, be transferred in horizontal quartz tube, pass into 8%O
2/ N
2mixed gas, with 10 DEG C of min
-1speed be warming up to 500 DEG C, keep after 6 hours, close heating, extract out silica tube, quick refrigeration is to room temperature.Grind to form 20-40 order size particles.
Catalyzer 2.0g, benzene 70mL and put into reaction vessel to methylbenzyl alcohol 2.5mL, connect reflux, put into the oil bath (85 DEG C) of preheating, starts to stir, and starts timing when waiting backflow phenomenon to occur, react after 15 minutes and stop, cooling.Getting 1 microlitre and carry out gas chromatographic analysis, is 100% to methylbenzyl alcohol transformation efficiency, is more than 90% to the selectivity of benzyl toluene.Through suction filtration by catalyst separating, filtrate decompression distilled, isolating the crude yield of benzyl toluene is 82%.
Embodiment 22
Adopt the catalyzer of embodiment 9.Catalyzer 2.0g, benzene 70mL and p-methoxybenzyl alcohol 2.5mL put into reaction vessel, connect reflux, put into the oil bath (85 DEG C) of preheating, start to stir, and start timing when waiting backflow phenomenon to occur, react after 55 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, p-methoxybenzyl alcohol transformation efficiency is 100%, is more than 97% to the selectivity of benzyl anisole.Through suction filtration by catalyst separating, filtrate decompression distilled, isolating the crude yield of benzyl anisole is 91%.
Embodiment 23
Adopt the catalyzer of embodiment 8.Catalyzer 2.0g, p-Xylol 70mL and put into reaction vessel to fluorophenyl methanol 3.5mL, connect reflux, put into the oil bath (145 DEG C) of preheating, starts to stir, and starts timing when waiting backflow phenomenon to occur, react after 55 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, the selectivity being 100%, 2-(4-luorobenzyl)-Isosorbide-5-Nitrae-dimethylbenzene to fluorophenyl methanol transformation efficiency is more than 93%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating 2-(4-luorobenzyl)-Isosorbide-5-Nitrae-dimethylbenzene is 80%.
Embodiment 24
After the catalyst filtration in embodiment 1, after chloroform and washing with alcohol, 110 DEG C of dryings 6 hours.Then according to the method synthesizing diphenyl methane compound of embodiment 1.Reuse 6 times, the yield after ditane is separated is respectively 90% (for the second time), 91% (for the third time), 93% (the 4th time), 90% (the 5th time) and 92% (the 6th time).
Comparative example 1
Prepared immobilized aluminum chloride catalyst according to patent (CN102329191A), preparation method is as follows.By the chitosan of 10g drying; 280mL anhydrous chloroform adds 500mL and is with in the there-necked flask of serpentine condenser; magnetic agitation; in bottle, logical nitrogen is after 1 hour; add 2.0g Aluminum chloride anhydrous, under nitrogen protection heating reflux reaction 3.5 days, after reaction terminates; solid is leached under nitrogen protection, and with anhydrous chloroform drip washing filter cake three times.Then vacuum-drying obtains filter cake 12.0g.
Get the immobilized aluminum chloride catalyst 2.0g of above-mentioned preparation, benzene 50mL and phenylcarbinol 2.5mL puts into reaction vessel, connects reflux, put into the oil bath (85 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 85%, and ditane selectivity is 78%.Through suction filtration by catalyst separating, filtrate decompression distilled, the crude yield isolating ditane is 57%.Reaction result is far below the catalyzer adopting preparation in the embodiment of the present invention 1.
Comparative example 2
Adopt molybdenum trioxide catalyst disclosed in document (Chemistry-A European Journal 15 (3): 742-753) report and patent JP2009067753.Preparation method is as follows.In the beaker of 2 liters, add the Ammonium Heptamolybdate [(NH of 15.0g
4) Mo
7o
244H
2o, molecular weight 1163.80], then add 500mL water, at room temperature stir 5 minutes.1L acetone is joined rapidly in above-mentioned solution.At room temperature continue reaction and leach solid after 7 minutes.After acetone (2 × 100mL) and Skellysolve A (2 × 20mL) washing, drying 14 hours in 60 DEG C of baking ovens.In 330oC air, roasting obtains this catalyzer in 2 hours.
Get the molybdenum trioxide catalyst 2.0g of above-mentioned preparation, methyl phenyl ketone 50mL and phenylcarbinol 4.5mL puts into reaction vessel, connects reflux, put into the oil bath (150 DEG C) of preheating, start to stir, when waiting backflow phenomenon to occur, start timing, react after 25 minutes and stop, cooling.Get 1 microlitre and carry out gas chromatographic analysis, phenylcarbinol transformation efficiency is 25%, and the selectivity of mixing (between neighbour to) benzyl methyl phenyl ketone is 10%.Reaction result is far below the catalyzer (embodiment 18) adopting preparation in the embodiment of the present invention 1.
Claims (14)
1. a preparation method for ditane compounds, the structural formula of prepared ditane compounds is shown below:
R
1and R
2for the substituting group of ortho position, a position or contraposition, be respectively-H ,-CH
3,-OCH
3,-CH
2cH
3,-CH (CH
3)
2,-C (=O) CH
3,-F ,-Cl ,-CF
3one in group;
Its synthetic route is as follows: in reaction vessel, add the one in benzene or substituted benzene, and substituted benzene is with following substituting group-CH on phenyl ring
3,-OCH
3,-CH
2cH
3,-CH (CH
3)
2,-C (=O) CH
3,-F ,-Cl ,-CF
3in a kind of benzene derivate;
Add with substituent compound on phenylcarbinol or phenylcarbinol benzene ring structure, substituting group is-CH again
3,-OCH
3,-CH
2cH
3,-CH (CH
3)
2,-C (=O) CH
3,-F ,-Cl ,-CF
3in one;
And catalyzer, isolate catalyzer after reaction, go out ditane compounds through fractionation by distillation;
Described catalyzer is M-V-O structure, and M is one or two or more kinds in Mo, Nb, W.
2. in accordance with the method for claim 1, it is characterized in that:
Described catalyzer is specifically as follows Mo-V-O, one or two or more kinds in W-V-O, Nb-V-O, Mo-W-V-O, Mo-Nb-V-O, W-Nb-V-O, Mo-W-Nb-V-O.
3. in accordance with the method for claim 1, it is characterized in that: it reacts at ambient pressure, temperature of reaction 80-150 DEG C; Reaction times is in 5-360 minute.
4. in accordance with the method for claim 3, it is characterized in that: preferably the reaction times is at 10-30 minute.
5. in accordance with the method for claim 1, it is characterized in that: with benzene or substituted benzene for reaction solvent, the usage quantity of catalyzer accounts for the 1-30% of reaction system gross weight; The phenyl ring of phenylcarbinol or phenylcarbinol is 1-60% with the volumetric concentration of substituent compound.
6. in accordance with the method for claim 5, it is characterized in that: with benzene or substituted benzene for reaction solvent, the usage quantity of catalyzer account for reaction system gross weight preferably use range be 3-10%.
7. in accordance with the method for claim 5, it is characterized in that: on the phenyl ring of phenylcarbinol or phenylcarbinol with substituent compound preferably volumetric concentration be 5-10%.
8., according to the method described in claim 1 or 2, it is characterized in that:
The preparation method of catalyzer is: by the presoma of one or two or more kinds in Mo, Nb, W presoma and V according to after certain mol proportion example fully ground and mixed, more than 300 DEG C, make this catalyzer after thermolysis; Described molar ratio is M/V is 1-6.
9. in accordance with the method for claim 8, it is characterized in that:
Molar ratio is M/V=2-4; Preferably heat decomposition temperature is 300 DEG C-600 DEG C.
10. in accordance with the method for claim 9, it is characterized in that: the molar ratio of M/V the best is 3.
11. in accordance with the method for claim 1, it is characterized in that:
When M is Mo, Nb and W, the molar ratio of any one amount of substance wherein between Mo, Nb, W and the amount of substance of whole Mo, Nb, W is not less than 0.1.
12. in accordance with the method for claim 8, it is characterized in that: on phenylcarbinol or phenylcarbinol phenyl ring with substituent compound, reaction raw materials transformation efficiency 100%, the separation yield more than 90% of ditane compounds;
Catalyzer can recycle more than 1 time, and activity and selectivity is constant.
13. in accordance with the method for claim 8, it is characterized in that: in the atmosphere of described thermolysis, the volumetric concentration of oxygen is 0 to 21%, and remaining gas can be one or two or more kinds in the rare gas elementes such as helium, nitrogen, argon gas.
14. in accordance with the method for claim 8, it is characterized in that:
Mo, Nb, W presoma is ammonium molybdate, potassium molybdate, Sodium orthomolybdate, molybdenum oxide, molybdenum chloride, niobium oxides, columbium pentachloride, ammonium niobium oxalate, wolframic acid, tungsten hexacarbonyl, ammonium tungstate, Tungsten oxide 99.999, and the presoma of V is ammonium meta-vanadate, vanadylic sulfate, vanadium acetylacetonate and vanadyl chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210224039.2A CN103508838B (en) | 2012-06-29 | 2012-06-29 | Preparation method of diphenylmethane compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210224039.2A CN103508838B (en) | 2012-06-29 | 2012-06-29 | Preparation method of diphenylmethane compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103508838A CN103508838A (en) | 2014-01-15 |
| CN103508838B true CN103508838B (en) | 2015-01-14 |
Family
ID=49892326
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210224039.2A Expired - Fee Related CN103508838B (en) | 2012-06-29 | 2012-06-29 | Preparation method of diphenylmethane compounds |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103508838B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288452A (en) * | 1998-01-15 | 2001-03-21 | Sk株式会社 | Method for preparing diarylethane |
| CN102029171A (en) * | 2010-11-17 | 2011-04-27 | 西北大学 | Catalyst for synthesizing diphenylmethane and preparation method thereof |
| CN102329191A (en) * | 2011-07-27 | 2012-01-25 | 浙江大学 | Method for preparing diphenyl methane or derivatives thereof |
-
2012
- 2012-06-29 CN CN201210224039.2A patent/CN103508838B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1288452A (en) * | 1998-01-15 | 2001-03-21 | Sk株式会社 | Method for preparing diarylethane |
| CN102029171A (en) * | 2010-11-17 | 2011-04-27 | 西北大学 | Catalyst for synthesizing diphenylmethane and preparation method thereof |
| CN102329191A (en) * | 2011-07-27 | 2012-01-25 | 浙江大学 | Method for preparing diphenyl methane or derivatives thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103508838A (en) | 2014-01-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Choudhary et al. | Solvent-free liquid phase oxidation of benzyl alcohol to benzaldehyde by molecular oxygen using non-noble transition metal containing hydrotalcite-like solid catalysts | |
| Deleplanque et al. | Production of acrolein and acrylic acid through dehydration and oxydehydration of glycerol with mixed oxide catalysts | |
| Tayebee et al. | An efficient and green synthetic protocol for the preparation of bis (indolyl) methanes catalyzed by H6P2W18O62· 24H2O, with emphasis on the catalytic proficiency of Wells-Dawson versus Keggin heteropolyacids | |
| Solhy et al. | Bi-functional modified-phosphate catalyzed the synthesis of α-α′-(EE)-bis (benzylidene)-cycloalkanones: Microwave versus conventional-heating | |
| Lee et al. | Efficient dehydration of methyl lactate to acrylic acid using Ca3 (PO4) 2–SiO2 catalyst | |
| CN103373978B (en) | Reaction method for preparing corresponding lactone, hydroxy acid and dicarboxylic acid through cyclic ketone oxidation | |
| Wei et al. | Solid superbase derived from lanthanum–magnesium composite oxide and its catalytic performance in the knoevenagel condensation under solvent-free condition | |
| Sun et al. | Synthesis and characterization of Pd based on [2, 2'-bipyridin]-4-amine functionalized nano cellulose as a novel and recyclable nano catalyst for Suzuki reaction | |
| AU2004240910B2 (en) | Phosphorus/vanadium catalyst preparation | |
| Yuan et al. | A Novel Brønsted-Lewis acidic catalyst based on heteropoly phosphotungstates: Synthesis and catalysis in benzylation of p-xylene with benzyl alcohol | |
| Liu et al. | Gold and silver nanoparticles supported on metal-organic frameworks: A highly active catalyst for three-component coupling reaction | |
| CN101786943A (en) | Catalytic synthesis method for preparing cresol by toluene one-step hydroxylation reaction | |
| CN114768877B (en) | Cellulose-loaded Cu 2 O/TiO 2 Catalytic material and method for applying catalytic material to boron addition reaction of p-benzoquinone methide | |
| CN103143381B (en) | Carbon-nitrogen material immobilized heteropoly acid catalyst and olefin epoxidation synthesis method | |
| Sanaei-Rad et al. | Hexamethylenetetramine-based ionic liquid anchored onto the metal–organic framework MIL-101 (Cr) as a superior and reusable heterogeneous catalyst for the preparation of hexahydroquinolines | |
| US20120149933A1 (en) | Ammoxidation catalyst and method for producing nitrile compound using the same | |
| CN104892682A (en) | Synthesis method of metal-coordination polymer containing sulfanilic acid and catalytic activity of metal-coordination polymer | |
| CN103508838B (en) | Preparation method of diphenylmethane compounds | |
| CN114289057A (en) | Nitrogen-doped carbon-iron-based nanoparticle catalyst, preparation method and application thereof in Friedel-crafts acylation reaction | |
| JP2012106942A (en) | Method for producing conjugated diene | |
| Feng et al. | Highly efficient chemoselective construction of 2, 2-dimethyl-6-substituted 4-piperidones via multi-component tandem Mannich reaction in ionic liquids | |
| CN113636939A (en) | Preparation method of 4,4' -dinitrobibenzyl | |
| CN113061145A (en) | Method for preparing chiral organic boron compound by catalyzing cellulose loaded copper and application | |
| CN101786016B (en) | Preparation method and application method of novel immobilized Lewis acid catalyst | |
| CN101337923B (en) | Process for purifying crude pyridine |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150114 Termination date: 20210629 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |