CN104262410B - A kind of synthetic method for being alkylated ferrocene derivatives - Google Patents
A kind of synthetic method for being alkylated ferrocene derivatives Download PDFInfo
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- CN104262410B CN104262410B CN201410521342.8A CN201410521342A CN104262410B CN 104262410 B CN104262410 B CN 104262410B CN 201410521342 A CN201410521342 A CN 201410521342A CN 104262410 B CN104262410 B CN 104262410B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
Abstract
The invention discloses a kind of synthetic method for being alkylated ferrocene derivatives, ferrocene, alkylating reagent, organic solvent is taken to be mixed with supported solid catalyst in addition autoclave, nitrogen is filled with normal temperature to 0.5~2.5MPa, airtight heating is to 80 DEG C~250 DEG C, stirring reaction 2~6 hours；Reaction terminates reaction mixture filtering, filtrate decompression distillation and concentration, alkylation ferrocene derivatives is made.The present invention solves traditional handicraft product and is difficult to the shortcomings of separation recycling, high pollution, deep-etching.Gained alkylferrocenes derivative can be used for that diesel oil is combustion-supporting and the field such as tail gas particle catcher regeneration.
Description
Technical field
The present invention relates to a kind of method of the synthesizing alkylated ferrocene derivatives of utilization solid acid catalyst.
Background technology
Ferrocene is also known as biscyclo pentadienyl iron, and it is a kind of metallo-organic compound with interlayer structure, in normal temperature
It is in orange crystal shape down, water insoluble, being soluble in the organic solvents such as diesel oil, gasoline, benzene, ethanol has chemical property stabilization, nothing
The features such as taste is nontoxic.Because Ferrocene and its derivative is widely used, as fume-eliminating energy-saving additive be usually used in gasoline, diesel oil,
The liquid fuels such as heavy diesel fuel, to saving the energy, reduction flue dust, preventing the pollution of the environment has positive effect.Ferrocene and its derivative
It is added in solid, liquid or gaseous fuel, its effect that is combustion-supporting, uprising and eliminating smoke can be played.After ferrocene is alkylated
Its solubility in diesel oil, gasoline can be significantly improved, and reduces required usage amount.
The preparation method of traditional alkylferrocenes is first to carry out acylation reaction, then reduce obtaining alkylferrocenes.Reduction
Reaction has a lot, and such as huang-Minlon reduction, Clemmenson reducing process, LiAlH4-AlCl3 mixtures reduction system, Zn-Hg are neat
Family name's reagent reducing process etc..The shortcoming of this method is exactly that synthesis step is complicated, and flow is cumbersome, not friendly enough to environment, is difficult point
From product etc..Can also one-step synthesis method alkylferrocenes, utilize Lewis acid, such as H3PO4、AlCl3Deng the alkane of progress ferrocene
Glycosylation reaction.The advantage of this method is that reaction condition is gentle, has the disadvantage big for environment pollution, product separation difficulty, catalyst
Cost is big, is not easy to industrialized production.
The loose equality people of height of Taiyuan Institure of Technology's department of chemistry engineering, using mol ratio as 1:1:0.75 ferrocene, bromoethane
And anhydrous Aluminum chloride, 6h is reacted at 38 DEG C, ethyl dicyclopentadienyl iron is successfully synthesized, yield is up to 77%.
Wang Yanxue, Bian Zhanxi of Chemistry and Chemical Engineering College of University of the Inner Mongol et al., equipped with agitator, condenser pipe, drying tube
There-necked flask in add 29.3g (0.22mol) finely ground aluminum trichloride (anhydrous), 100ml dichloroethanes is instilled under agitation
32.7g (0.22mol) oenanthyl chloro, stirs 15min, standby.37.2g (0.20mol) ferrocene is added in another there-necked flask,
250ml dichloroethanes, stirring after dissolving, instills above-mentioned acyl chlorides-aluminum chloride complex solution under frozen water cooling, drips Bi Sheng
Warm to 50 DEG C reaction 6h (whether complete with thin-layered chromatography detection reaction).Mixed liquor is poured into frozen water.Separate organic phase, water
Extracted with dichloroethanes.Merge organic phase, successively with water, saturated sodium carbonate, water washing, vacuum distillation is obtained except solvent after drying
Red solid.90g zinc powders are used again, and Zn-Hg Qi Shi reagents are made in 8.2g mercury chloride, 6ml concentrated hydrochloric acids, 125ml water.Add 500ml
Benzene, 50ml methanol and above-mentioned acyl Ferrocene crude product.Stirring, is heated to reflux the dense HCl of 100ml that drip, is stirred at reflux 5~7h,
Reaction process is monitored with thin-layer chromatography.After the completion of reaction, cooling, suction filtration, Zn-Hg Qi Shi reagents are washed with benzene, are merged, have been separated
Machine phase.Water, 5% sodium carbonate liquor, water washing are used successively, solvent are evaporated off after drying, vacuum distillation obtains brown liquid.The party
Method ultimate yield is 30%-70%, but needs two steps to complete, and each step is required for expending substantial amounts of acid waste liquid, dirty to environment
Dye is big.Above method face it is common the problem of be liquid acid for equipment corrosion is serious, waste liquid is big for environment pollution, catalysis
Agent can not recycling etc..
As recent industrial is developed rapidly, problem of environmental pollution is increasingly serious, the preventing and treating of especially city PM2.5 pollutions
The demand of motor-vehicle tail-gas improvement product will be greatly increased.Ferrocene and derivative as classical fuel oil additive, its
Demand will also be greatly increased.The processing step of the existing synthesizing alkylated ferrocene derivatives of utilization ferrocene is numerous and diverse, to environment
Influence is big.Therefore, in the urgent need to a kind of inexpensive, environment-friendly synthesis technique.
The content of the invention
Alkylation ferrocene derivatives are catalyzed and synthesized it is an object of the invention to provide a kind of utilization solid acid catalyst
New process.By controlling various process conditions, the purpose of the fragrant cycloalkylation of efficient catalytic ferrocene is reached.
In order to achieve the above object, the technical scheme is that：
A kind of synthetic method for being alkylated ferrocene derivatives, the alkylation ferrocene derivatives are the cyclopentadienyls of monoalkylation two
The mixture of iron derivative and many alkylation ferrocene derivatives, the monoalkylation ferrocene derivatives are the rings in ferrocene
There are the ferrocene derivatives of 1 substitution alkyl on pentadienyl, many alkylation ferrocene derivatives are the rings in ferrocene
There are the ferrocene derivatives of 2~3 substitution alkyl on pentadienyl；Monoalkylation ferrocene derivatives and many alkylation ferrocene
Substitution alkyl in derivative is identical, and the substitution alkyl is C1~C8Alkyl；Methods described is：
Ferrocene, alkylating reagent, organic solvent is taken to be mixed with supported solid catalyst in addition autoclave, often
Nitrogen is filled with temperature to 0.5~2.5MPa, airtight heating to 80 DEG C~250 DEG C, stirring reaction 2~6 hours；Reaction terminates reaction
Mixed liquor filtering, filtrate decompression distillation and concentration, obtained alkylation ferrocene derivatives；
Described alkylating reagent is C1~C8Alkene or C1~C8Fatty alcohol, the corresponding obtained cyclopentadienyl of monoalkylation two
The carbon number of iron derivative and each substitution alkyl on many alkylation ferrocene derivatives is identical with the carbon number of alkylating reagent；
The ratio between the ferrocene, amount of material of alkylating reagent are 1：1~13, preferably 1：2~10.
Described load-type solid acid catalyst is made up of carrier and the acid catalyst being carried on carrier, and load capacity is
10%~75%, preferably 25~75%, the acid catalyst is phosphoric acid, sulfuric acid, AlCl3Or heteropoly acid, the heteropoly acid is preferred
Phosphotungstic acid or phosphomolybdic acid；The carrier is aluminum oxide, silica gel or diatomite, preferably aluminum oxide or silica gel；.
The quality of described load-type solid acid catalyst and the mass ratio of ferrocene are 0.1~1：1, preferably 0.5：1；
Described organic solvent is benzene,toluene,xylene or trimethylbenzene, preferably toluene or trimethylbenzene, most preferably toluene；Institute
State the 5-20mL/g that the volumetric usage of organic solvent is calculated as with the quality consumption of ferrocene；
The vacuum distillation can the vacuum distillation at a temperature of 80 DEG C, removing solvent and unreacted raw material, obtained target production
Thing is alkylated ferrocene derivatives.Distilling obtained solvent can recycle.
During the reaction, mixing speed is preferably 60~500r/min.
The temperature of the reaction is preferably 100~250 DEG C, more preferably 120~230 DEG C, most preferably 180~230 DEG C.
The pressure that nitrogen is filled with the normal temperature is 0.5~2.5MPa, preferably 1MPa.
Preferably 4~5 hours time of the reaction.
The catalyst used in the inventive method is solid catalyst, can use fine catalyst or preformed catalyst
.Solid catalyst will not dissolve in reaction solution, be also insoluble in the liquid phase generated in course of reaction, can simple separation, return
Receive, recycle.
The catalyst of the present invention can be bought or voluntarily prepare, the preparation being well known to those skilled in the art from market
Method.Specifically, the load-type solid acid catalyst used in the present invention can be prepared by full volumetric infusion process.
Target product of the present invention is the mixture of monoalkylation ferrocene derivatives and many alkylation ferrocene derivatives, many
Alkylation ferrocene derivatives are that alkylated reaction generation further occurs for monoalkylation ferrocene derivatives.All alkylations two
Luxuriant iron derivative can be used as the main component of purifying vehicle exhaust fuel oil additive, therefore all alkylation ferrocene spread out
Biology is the target product of this reaction.The present invention need not spread out monoalkylation ferrocene derivatives and many alkylation ferrocene
Biology is individually separated.
In monoalkylation ferrocene derivatives produced by the present invention and many alkylation ferrocene derivatives, replace the carbon of alkyl
Number is identical with the carbon number of alkylating reagent, i.e., when alkylating reagent is butanol or butylene, and obtained product is butyl ferrocene.Alkane
When base reagent is ethanol, obtained product is ethyl dicyclopentadienyl iron.When alkylating reagent is hexene, obtained product is hexyl two
Luxuriant iron.
When carbochain is more than three, there is isomer, such as butanol has n-butanol, isobutanol, the tert-butyl alcohol, carrying out
During alkylation substitution, the carbon-chain structure of substitution alkyl may can be reset, and obtain more stable substitution product.The present invention is ground
Study carefully and show, according to the mechanism of alkylated reaction, intermediate product carbonium ion can be produced in course of reaction.Weight can occur for carbonium ion
Row, according to the result of study of the present invention, during using isobutanol and isobutene for alkylating reagent, reaction product is also the tert-butyl group two
Luxuriant iron.
The present invention is stressed that, although the carbon-chain structure of substitution alkyl may be reset, but the carbon of substitution alkyl
Number be still to maintain with alkylating reagent identical, though substitution alkyl be which kind of isomers, alkyl substitution product is this hair
Bright target product, the isomery change of substitution alkyl does not influence the implementation of the present invention program, and the purpose of the inventive method is to prepare
Ferrocene derivatives are alkylated, is not concerned with wherein replacing the specific heterogeneous structure of alkyl, is kept and alkyl in substitution alkyl carbon number
Change in the case of reagent identical, any isomers alkyl is the target product of the present invention.
The preferred isobutanol of alkylating reagent of the present invention, isobutene or the tert-butyl alcohol, obtained alkylation ferrocene spread out
Biology is tert-butyl group ferrocene.
Alkylation ferrocene derivatives produced by the present invention, which can be applied, is used as purifying vehicle exhaust fuel oil additive.
When alkylation ferrocene derivatives of the present invention are as purifying vehicle exhaust fuel oil additive, for the ease of this hair
The quick mixed dissolution of bright product and vehicle fuel, in last handling process, during filtrate decompression distillation and concentration, can retain a small amount of molten
Agent, can so be directly appended in gasoline as fuel oil additive use.
The present invention is developed for current process step is numerous and diverse, flow is more, the shortcomings of there is problem of environmental pollution, energy
Effectively realize that the simple separations such as catalyst, raw material, product are reclaimed, reaction conversion ratio, selectivity are all very high, are especially suitable for actual work
Industry application.The present invention solves traditional handicraft product and is difficult to the shortcomings of separation recycling, high pollution, deep-etching.Gained alkyl two
Luxuriant iron derivative can be used for that diesel oil is combustion-supporting and the field such as tail gas particle catcher regeneration.
Embodiment
With specific embodiment, the present invention will be further described below, but protection scope of the present invention not limited to this.
The catalyst used in the embodiment of the present invention is prepared or bought as follows：
Carrier loaded heteropoly acid is prepared by equi-volume impregnating, and the preparation method of such as alumina load phosphotungstic acid is as follows：
Take 10gAl2O3Particle, the phosphotungstic acid for weighing 4.3g is dissolved in deionized water and is configured to 12ml maceration extracts.Maceration extract is dripped to load dropwise
On body, stirred when being added dropwise, make maceration extract that carrier is completely covered, 4h is impregnated at room temperature.Then it is dried overnight again at 120 DEG C, most
After be calcined 4h, obtain alumina catalyst load phosphotungstic acid, load capacity is 30%.
The preparation method of other carrier loaded heteropolyacid catalysts is identical.Different carriers can be used instead includes silica gel and diatomite
Deng.Heteropoly acid can change phosphotungstic acid into phosphomolybdic acid, alumina load phosphomolybdic acid be made, load capacity is 30%.
Carrier loaded phosphoric acid, sulfuric acid, AlCl3Prepared again by equi-volume impregnating, step is ibid.Silica gel is made respectively
Phosphoric acid (load capacity 25%), silica gel load phosphoric acid (load capacity 50%), silica gel load phosphoric acid (load capacity 75%), silica gel is loaded to bear
Carry sulfuric acid (load capacity 50%), silica gel load alchlor (load capacity 40%).For in following examples.
Embodiment 1
This example is using ferrocene as raw material, and with silica gel load phosphoric acid (load capacity 25%) for catalyst, toluene is solvent, different
Butanol is alkylating reagent.
Reactor volume：100ml
Ferrocene：2g
Catalyst：1g
Alkylating reagent：4g
Toluene：20ml
Reaction temperature：120℃
Nitrogen pressure：1MPa
Reaction time：4h
Stir speed (S.S.)：500r/min
Reaction is carried out in 100ml autoclaves, and charge and discharge nitrogen is multiple before reaction, the air of residual in displacement kettle, and is filled
Enter 1MPa nitrogen and keep kettle inner high voltage force environment.Stir and be raised to 120 DEG C of reaction temperature according to 5 DEG C/min speed.React 4h
Afterwards, heating is stopped, slow release nitrogen after cooling, through filtering, obtained filtrate is raw material and product mixtures.The mixture
Most solvent and alkylating reagent can be removed by 80 DEG C of vacuum distillations, the target product concentrated is (containing a small amount of molten
Agent), it can be directly used for producing purifying vehicle exhaust fuel oil additive.
Enriched product after terminating to reaction carries out GC-MS analyses, and the yield of confirmation form tert-butyl group ferrocene is 25%, many
The yield of tert-butyl group ferrocene is 5%, and the total recovery of tert-butyl group ferrocene is 30%.
Embodiment 2
This example is using ferrocene as raw material, and with silica gel load phosphoric acid (load capacity 50%) for catalyst, trimethylbenzene is solvent,
Isobutene is alkylating reagent.
Reactor volume：100ml
Ferrocene：2g
Catalyst：1g
Alkylating reagent：8g
Trimethylbenzene：20ml
Reaction temperature：180℃
Nitrogen pressure：1MPa
Reaction time：4h
Stir speed (S.S.)：500r/min
Reaction is carried out in 100ml autoclaves, and charge and discharge nitrogen is multiple before reaction, the air of residual in displacement kettle, and is filled
Enter 1MPa nitrogen and keep kettle inner high voltage force environment.Stir and be raised to 180 DEG C of reaction temperature according to 5 DEG C/min speed.React 4h
Afterwards, heating is stopped, slow release nitrogen after cooling, through filtering, obtained filtrate is raw material and product mixtures.The mixture
Most solvent and alkylating reagent can be removed by 80 DEG C of vacuum distillations, the target product concentrated is (containing a small amount of molten
Agent), it can be directly used for producing purifying vehicle exhaust fuel oil additive.
Enriched product after terminating to reaction carries out GC-MS analyses, and the yield of confirmation form tert-butyl group ferrocene is 85%, many
The yield of tert-butyl group ferrocene is 10%, and the total recovery of tert-butyl group ferrocene is 95%.
Embodiment 3
This example is using ferrocene as raw material, and with silica gel load phosphoric acid (load capacity 75%) for catalyst, toluene is solvent, uncle
Butanol is alkylating reagent.
Reactor volume：100ml
Ferrocene：2g
Catalyst：1g
Alkylating reagent：2g
Toluene：20ml
Reaction temperature：230℃
Nitrogen pressure：1MPa
Reaction time：4h
Stir speed (S.S.)：500r/min
Reaction is carried out in 100ml autoclaves, and charge and discharge nitrogen is multiple before reaction, the air of residual in displacement kettle, and is filled
Enter 1MPa nitrogen and keep kettle inner high voltage force environment.Stir and be raised to 230 DEG C of reaction temperature according to 5 DEG C/min speed.React 4h
Afterwards, heating is stopped, slow release nitrogen after cooling, through filtering, obtained filtrate is raw material and product mixtures.The mixture
Most solvent and alkylating reagent can be removed by 80 DEG C of vacuum distillations, the target product concentrated is (containing a small amount of molten
Agent), it can be directly used for producing purifying vehicle exhaust fuel oil additive.
Enriched product after terminating to reaction carries out GC-MS analyses, and the yield of confirmation form tert-butyl group ferrocene is 75%, many
The yield of tert-butyl group ferrocene is 7%, and the total recovery of tert-butyl group ferrocene is 82%.
Embodiment 4
This example is using ferrocene as raw material, and with silica gel load sulfuric acid (load capacity 50%) for catalyst, toluene is solvent, second
Alcohol is alkylating reagent.
Reactor volume：100ml
Ferrocene：2g
Catalyst：1g
Alkylating reagent：4g
Toluene：20ml
Reaction temperature：180℃
Nitrogen pressure：1MPa
Reaction time：4h
Stir speed (S.S.)：500r/min
Reaction is carried out in 100ml autoclaves, and charge and discharge nitrogen is multiple before reaction, the air of residual in displacement kettle, and is filled
Enter 1MPa nitrogen and keep kettle inner high voltage force environment.Stir and be raised to 180 DEG C of reaction temperature according to 5 DEG C/min speed.React 4h
Afterwards, heating is stopped, slow release nitrogen after cooling, through filtering, obtained filtrate is raw material and product mixtures.The mixture
Most solvent and alkylating reagent can be removed by 80 DEG C of vacuum distillations, the target product concentrated is (containing a small amount of molten
Agent), it can be directly used for producing purifying vehicle exhaust fuel oil additive.
Enriched product after terminating to reaction carries out GC-MS analyses, and the yield of confirmation form ethyl dicyclopentadienyl iron is 45%, many second
The yield of base ferrocene is 4.5%, and the total recovery of ethyl dicyclopentadienyl iron is 49.5%.
Embodiment 5
This example is using ferrocene as raw material, with silica gel load alchlor (load capacity 40%) for catalyst, and toluene is molten
Agent, hexene is alkylating reagent.
Reactor volume：100ml
Ferrocene：2g
Catalyst：1g
Alkylating reagent：4g
Toluene：20ml
Reaction temperature：180℃
Nitrogen pressure：1MPa
Reaction time：4h
Stir speed (S.S.)：500r/min
Reaction is carried out in 100ml autoclaves, and charge and discharge nitrogen is multiple before reaction, the air of residual in displacement kettle, and is filled
Enter 1MPa nitrogen and keep kettle inner high voltage force environment.Stir and be raised to 180 DEG C of reaction temperature according to 5 DEG C/min speed.React 4h
Afterwards, heating is stopped, slow release nitrogen after cooling, through filtering, obtained filtrate is raw material and product mixtures.The mixture
Most solvent and alkylating reagent can be removed by 80 DEG C of vacuum distillations, the target product concentrated is (containing a small amount of molten
Agent), it can be directly used for producing purifying vehicle exhaust fuel oil additive.
Enriched product after terminating to reaction carries out GC-MS analyses, and the yield of confirmation form hexyl ferrocene is 40%, more oneself
The yield of base ferrocene is 3%, and the total recovery of hexyl ferrocene is 43%.
Embodiment 6
This example is using ferrocene as raw material, and using alumina load phosphotungstic acid (load capacity is 30%) for catalyst, toluene is
Solvent, the tert-butyl alcohol is alkylating reagent.
Reactor volume：100ml
Ferrocene：2g
Catalyst：1g
Alkylating reagent：4g
Toluene：20ml
Reaction temperature：180℃
Nitrogen pressure：1MPa
Reaction time：4h
Stir speed (S.S.)：500r/min
Reaction is carried out in 100ml autoclaves, and charge and discharge nitrogen is multiple before reaction, the air of residual in displacement kettle, and is filled
Enter 1MPa nitrogen and keep kettle inner high voltage force environment.Stir and be raised to 180 DEG C of reaction temperature according to 5 DEG C/min speed.React 4h
Afterwards, heating is stopped, slow release nitrogen after cooling, through filtering, obtained filtrate is raw material and product mixtures.The mixture
Most solvent and alkylating reagent can be removed by 80 DEG C of vacuum distillations, the target product concentrated is (containing a small amount of molten
Agent), it can be directly used for producing purifying vehicle exhaust fuel oil additive.
Enriched product after terminating to reaction carries out GC-MS analyses, and the yield of confirmation form tert-butyl group ferrocene is 65%, many
The yield of tert-butyl group ferrocene is 22%, and the total recovery of tert-butyl group ferrocene is 87%.
Embodiment 7
This example is using ferrocene as raw material, and using alumina load phosphomolybdic acid (load capacity is 30%) for catalyst, toluene is
Solvent, the tert-butyl alcohol is alkylating reagent.
Reactor volume：100ml
Ferrocene：2g
Catalyst：1g
Alkylating reagent：4g
Toluene：20ml
Reaction temperature：230℃
Nitrogen pressure：1MPa
Reaction time：4h
Stir speed (S.S.)：500r/min
Reaction is carried out in 100ml autoclaves, and charge and discharge nitrogen is multiple before reaction, the air of residual in displacement kettle, and is filled
Enter 1MPa nitrogen and keep kettle inner high voltage force environment.Stir and be raised to 230 DEG C of reaction temperature according to 5 DEG C/min speed.React 4h
Afterwards, heating is stopped, slow release nitrogen after cooling, through filtering, obtained filtrate is raw material and product mixtures.The mixture
Most solvent and alkylating reagent can be removed by 80 DEG C of vacuum distillations, the target product concentrated is (containing a small amount of molten
Agent), it can be directly used for producing purifying vehicle exhaust fuel oil additive.
Enriched product after terminating to reaction carries out GC-MS analyses, and the yield of confirmation form tert-butyl group ferrocene is 65%, many
The yield of tert-butyl group ferrocene is 21%, and the total recovery of tert-butyl group ferrocene is 86%.
1-7 of embodiment of the present invention target product total recovery such as table 1 below：
Table 1
Claims (7)
1. a kind of synthetic method for being alkylated ferrocene derivatives, the alkylation ferrocene derivatives are monoalkylation ferrocene
The mixture of derivative and many alkylation ferrocene derivatives, the monoalkylation ferrocene derivatives are the rings penta in ferrocene
There are the ferrocene derivatives of 1 substitution alkyl on dialkylene, many alkylation ferrocene derivatives are the rings penta in ferrocene
There are the ferrocene derivatives of 2~3 substitution alkyl on dialkylene；Described monoalkylation ferrocene derivatives are the cyclopentadienyl of the tert-butyl group two
Iron, described many alkylation ferrocene derivatives are many tert-butyl group ferrocene；It is characterized in that methods described is：
Ferrocene, alkylating reagent, organic solvent is taken to be mixed with load-type solid acid catalyst in addition autoclave, normal temperature
Under be filled with nitrogen to 0.5~2.5MPa, airtight heating to 80 DEG C~250 DEG C, stirring reaction 2~6 hours；It is mixed that reaction terminates reaction
Close liquid filtering, filtrate decompression distillation and concentration, alkylation ferrocene derivatives are made；
Described alkylating reagent is the tert-butyl alcohol,
The ratio between the ferrocene, amount of material of alkylating reagent are 1：1~13；
The load-type solid acid catalyst is made up of carrier and the acid catalyst that is carried on carrier, and load capacity is 25~
75%, the acid catalyst is heteropoly acid, and the heteropoly acid is phosphotungstic acid or phosphomolybdic acid；The carrier is aluminum oxide.
2. the method as described in claim 1, it is characterised in that the ratio between the ferrocene, amount of material of alkylating reagent are 1：
2~10.
3. the method as described in claim 1, it is characterised in that the quality and ferrocene of described load-type solid acid catalyst
Mass ratio be 0.1~1：1.
4. the method as described in claim 1, it is characterised in that described organic solvent is benzene,toluene,xylene or trimethylbenzene.
5. the method as described in claim 1, it is characterised in that the volumetric usage of the organic solvent is used with the quality of ferrocene
Measure the 5-20mL/g being calculated as.
6. the method as described in claim 1, it is characterised in that the filtrate decompression distills the vacuum distillation at a temperature of 80 DEG C, removes
Solvent and unreacted raw material are removed, target product alkylation ferrocene derivatives are made.
7. the method as described in claim 1, it is characterised in that the temperature of the reaction is 120~230 DEG C.
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