CN107011390B - A kind of synthetic method being alkylated ferrocene derivatives - Google Patents
A kind of synthetic method being alkylated ferrocene derivatives Download PDFInfo
- Publication number
- CN107011390B CN107011390B CN201710312200.4A CN201710312200A CN107011390B CN 107011390 B CN107011390 B CN 107011390B CN 201710312200 A CN201710312200 A CN 201710312200A CN 107011390 B CN107011390 B CN 107011390B
- Authority
- CN
- China
- Prior art keywords
- ferrocene
- reaction
- derivatives
- ferrocene derivatives
- alkylating reagent
- 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.)
- Active
Links
Classifications
-
- 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 methods for being alkylated ferrocene derivatives, it takes ferrocene, alkylating reagent, organic solvent to mix with supported solid catalyst to be added in autoclave, nitrogen is filled under room temperature to 0.5~2.5MPa, airtight heating is to 80 DEG C~250 DEG C, and the reaction was stirred for 2 to 6 hours；Reaction reaction was completed mixed liquor filtering, filtrate decompression distillation and concentration are made and are alkylated ferrocene derivatives.The present invention solves traditional handicraft product and is difficult to the disadvantages of separating recycling, high pollution, deep-etching.Gained alkylferrocenes derivative can be used for the fields such as diesel oil is combustion-supporting and tail gas particle catcher regenerates.
Description
The application is application number 2014105213428, and the applying date on 09 30th, 2014, a kind of entitled alkylation two was luxuriant
The divisional application of the synthetic method patent application of iron derivative
Technical field
The present invention relates to a kind of methods using the synthesizing alkylated ferrocene derivatives of solid acid catalyst.
Background technique
Ferrocene is also known as biscyclo pentadienyl iron, it is a kind of metallo-organic compound with interlayer structure, in room temperature
It is down in orange crystal shape, it is not soluble in water, the organic solvents such as diesel oil, gasoline, benzene, ethyl alcohol are soluble in chemical property stabilization, nothing
The features such as taste is nontoxic.Since 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 energy saving, 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, restores again to obtain alkylferrocenes.Reduction
Reaction has very much, as huang-Minlon reduction, Clemmenson reduction method, LiAlH4-AlCl3 mixture reduction system, Zn-Hg are neat
Family name's reagent reduction method etc..The shortcomings that this method is exactly synthesis step complexity, and process is cumbersome, not friendly enough to environment, is not easy point
From product etc..Lewis acid, such as H can also be utilized with one-step synthesis method alkylferrocenes3PO4、AlCl3Deng carrying out the alkane of ferrocene
Glycosylation reaction.The advantages of this method is that reaction condition is mild, the disadvantage is that causing serious pollution to the environment, product separation is difficult, catalyst
Cost is big, is not easy to industrialized production.
The loose equality people of the height of Taiyuan Institure of Technology's department of chemistry engineering, ferrocene, bromoethane with molar ratio for 1:1:0.75
And anhydrous aluminum chloride, 6h is reacted at 38 DEG C, successfully synthesizes ethyl dicyclopentadienyl iron, yield is up to 77%.
Wang Yanxue, Bian Zhanxi et al. of Chemistry and Chemical Engineering College, University of the Inner Mongol are being equipped with blender, condenser pipe, drying tube
There-necked flask in 29.3g (0.22mol) finely ground aluminum trichloride (anhydrous) is added, 100ml dichloroethanes instills under stiring
32.7g (0.22mol) oenanthyl chloro stirs 15min, spare.37.2g (0.20mol) ferrocene is added in another there-necked flask,
250ml dichloroethanes, stirring after dissolution, instill above-mentioned acyl chlorides-aluminum chloride complex solution in the case where ice water is cooling, drip Bi Sheng
Whether temperature is to 50 DEG C of reaction 6h (complete with thin-layered chromatography detection reaction).Mixed liquor is poured into ice water.Separate organic phase, water
Mutually extracted with dichloroethanes.Merge organic phase, successively uses water, saturated sodium carbonate, water washing, be evaporated under reduced pressure after dry except solvent obtains
Red solid.90g zinc powder is used again, and 8.2g mercury chloride, 6ml concentrated hydrochloric acid, Zn-Hg Qi Shi reagent is made in 125ml water.500ml is added
Benzene, 50ml methanol and above-mentioned acyl Ferrocene crude product.Stirring, is heated to reflux the dense HCl of the 100ml that drips, is stirred at reflux 5~7h,
Reaction process is monitored with thin-layer chromatography.After the reaction was completed, cooling, it filters, Zn-Hg Qi Shi reagent is washed with benzene, is merged, has been separated
Machine phase.Water, 5% sodium carbonate liquor, water washing are successively used, solvent is evaporated off after dry, is evaporated under reduced pressure to brown liquid.The party
Method ultimate yield is 30%-70%, but two steps is needed to complete, and each step requires to expend a large amount of acid waste liquid, to environment dirt
Dye is big.The common problem that above method faces is that liquid acid causes serious pollution to the environment for equipment seriously corroded, waste liquid, is catalyzed
Agent is non-recyclable and reusable etc..
With the rapid development of recent industry, environmental pollution is getting worse, the prevention and treatment of especially city PM2.5 pollution
The demand of motor-vehicle tail-gas improvement product will be greatly increased.The fuel oil additive of ferrocene and derivative as classics,
Demand will also greatly increase.The existing processing step using the synthesizing alkylated ferrocene derivatives of ferrocene is many and diverse, to environment
It influences big.Therefore, there is an urgent need to a kind of low costs, environmental-friendly synthesis technology.
Summary of the invention
Alkylation ferrocene derivatives are catalyzed and synthesized using solid acid catalyst the purpose of the present invention is to provide a kind of
New process.By controlling various process conditions, reach the alkylated purpose of efficient catalytic ferrocene aromatic rings.
In order to achieve the above object, the technical solution of the present invention is as follows:
A kind of synthetic method being alkylated ferrocene derivatives, the alkylation ferrocene derivatives are two cyclopentadienyls of monoalkylation
The mixture of iron derivative and more alkylation ferrocene derivatives, the monoalkylation ferrocene derivatives are the rings in ferrocene
There are the ferrocene derivatives of 1 substitution alkyl on pentadienyl, more alkylation ferrocene derivatives are the rings in ferrocene
There are the ferrocene derivatives of 2~3 substitution alkyl on pentadienyl；Monoalkylation ferrocene derivatives and more alkylation ferrocene
Substitution alkyl in derivative is identical, and the substitution alkyl is C1~C8Alkyl；The method are as follows:
It takes ferrocene, alkylating reagent, organic solvent to mix with supported solid catalyst to be added in autoclave, often
Nitrogen is filled under temperature to 0.5~2.5MPa, airtight heating is to 80 DEG C~250 DEG C, and the reaction was stirred for 2 to 6 hours；Reaction was completed for reaction
Alkylation ferrocene derivatives are made in mixed liquor filtering, filtrate decompression distillation and concentration；
The alkylating reagent is C1~C8Alkene or C1~C8Fatty alcohol, corresponding obtained two cyclopentadienyl of monoalkylation
The carbon number of iron derivative and each substitution alkyl on more alkylation ferrocene derivatives is identical as the carbon number of alkylating reagent；
The ratio between amount of substance of the ferrocene, alkylating reagent is 1:1~13, preferably 1:2~10.
The load-type solid acid catalyst is made 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 are preferred
Phosphotungstic acid or phosphomolybdic acid；The carrier is aluminium oxide, silica gel or diatomite, preferably aluminium oxide or silica gel；.
The quality of the load-type solid acid catalyst and the mass ratio of ferrocene are 0.1~1:1, preferably 0.5:1；
The 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 dosage of ferrocene；
The vacuum distillation can be evaporated under reduced pressure at a temperature of 80 DEG C, remove solvent and unreacted raw material, and target is made and produces
Object is alkylated ferrocene derivatives.Distilling obtained solvent can recycle.
When the reaction, mixing speed is preferably 60~500r/min.
The temperature of the reaction is preferably 100~250 DEG C, more preferable 120~230 DEG C, most preferably 180~230 DEG C.
The pressure that nitrogen is filled under the room temperature is 0.5~2.5MPa, preferably 1MPa.
The time of the reaction preferably 4~5 hours.
Catalyst used in the method for the present invention is solid catalyst, and fine catalyst or preformed catalyst can be used
?.Solid catalyst will not dissolve in reaction solution, be also insoluble in the liquid phase generated in reaction process, can simple separation, return
It receives, recycle.
Catalyst of the invention can be bought from market or voluntarily be prepared, the preparation being well known to those skilled in the art
Method.Specifically, 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 more alkylation ferrocene derivatives, more
Ferrocene derivatives are alkylated as the generation of monoalkylation ferrocene derivatives further occurrence alkylated reaction.All alkylations two
The main component that luxuriant iron derivative can be used as purifying vehicle exhaust fuel oil additive uses, therefore all alkylation ferrocene spread out
Biology is the target product of this reaction.The present invention does not need to spread out monoalkylation ferrocene derivatives and more alkylation ferrocene
Biology is individually separated.
In monoalkylation ferrocene derivatives produced by the present invention and more alkylation ferrocene derivatives, replace the carbon of alkyl
Number is identical as the carbon number of alkylating reagent, i.e., when alkylating reagent is butanol or butylene, obtained product is butyl ferrocene.Alkane
When base reagent is ethyl alcohol, obtained product is ethyl dicyclopentadienyl iron.When alkylating reagent is hexene, obtained product is hexyl two
Luxuriant iron.
For carbochain at three or more, there are isomers, such as butanol, have n-butanol, isobutanol, the tert-butyl alcohol, are carrying out
When alkylation replaces, replaces the carbon-chain structure of alkyl that may can reset, obtain more stable substitution product.The present invention is ground
Study carefully the mechanism shown according to alkylated reaction, intermediate product carbonium ion can be generated in reaction process.Weight can occur for carbonium ion
Row, when result of study according to the present invention using isobutanol and isobutene is alkylating reagent, reaction product is also tert-butyl two
Luxuriant iron.
Although the present invention it is emphasized that replace alkyl carbon-chain structure may reset, replace alkyl carbon
Number be still to maintain it is identical with alkylating reagent, though substitutions alkyl be which kind of isomers, alkyl substitution product is this hair
Bright target product replaces the isomery of alkyl to change the implementation for not influencing the present invention program, and the purpose of the method for the present invention is to prepare
Ferrocene derivatives are alkylated, the specific heterogeneous structure for wherein replacing alkyl is not concerned with, are replacing alkyl carbon number to keep and alkyl
Change in the identical situation of reagent, any isomers alkyl is target product of the invention.
The preferred isobutanol of alkylating reagent of the present invention, isobutene or the tert-butyl alcohol, alkylation ferrocene obtained spread out
Biology is tert-butyl ferrocene.
Alkylation ferrocene derivatives produced by the present invention can be using 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 when filtrate decompression distillation and concentration, can retain a small amount of molten in last handling process
Agent can be directly appended in gasoline use as fuel oil additive in this way.
The present invention is for the disadvantages of current process step is many and diverse, process is more, there are problem of environmental pollutions exploitation, energy
Effectively realize the recycling of the simple separations such as catalyst, raw material, product, reaction conversion ratio, selectivity are all very high, are very suitable to practical work
Industry application.The present invention solves traditional handicraft product and is difficult to the disadvantages of separating recycling, high pollution, deep-etching.Gained alkyl two
Luxuriant iron derivative can be used for the fields such as diesel oil is combustion-supporting and tail gas particle catcher regenerates.
Specific embodiment
With specific embodiment, the present invention will be further described below, and but the scope of the present invention is not limited thereto.
Catalyst used in the embodiment of the present invention is prepared or is bought as follows:
Carrier loaded heteropoly acid by equi-volume impregnating prepare, as alumina load phosphotungstic acid the preparation method is as follows:
Take 10gAl2O3Particle, the phosphotungstic acid for weighing 4.3g are dissolved in deionized water and are configured to 12ml maceration extract.Maceration extract is dripped to load dropwise
On body, is stirred when being added dropwise, make maceration extract that carrier be completely covered, impregnate 4h at room temperature.Then it is dried overnight at 120 DEG C again, most
After roast 4h, obtain alumina catalyst load phosphotungstic acid, load capacity 30%.
The preparation method of other carrier loaded heteropolyacid catalysts is identical.It includes silica gel and diatomite that different carriers can be used instead
Deng.Heteropoly acid can change phosphotungstic acid into phosphomolybdic acid, and alumina load phosphomolybdic acid, load capacity 30% is made.
Carrier loaded phosphoric acid, sulfuric acid, AlCl3Same to be prepared by equi-volume impregnating, step is same as above.Silica gel is made respectively
Load phosphoric acid (load capacity 25%), silica gel load phosphoric acid (load capacity 50%), silica gel load phosphoric acid (load capacity 75%), silica gel are negative
Carry sulfuric acid (load capacity 50%), silica gel load alchlor (load capacity 40%).For in following embodiment.
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.
Reaction kettle volume: 100ml
Ferrocene: 2g
Catalyst: 1g
Alkylating reagent: 4g
Toluene: 20ml
Reaction temperature: 120 DEG C
Nitrogen pressure: 1MPa
Reaction time: 4h
Stirring rate: 500r/min
Reaction carries out in 100ml autoclave, and charge and discharge nitrogen is multiple before reacting, and replaces remaining air in autoclave body, and fill
Enter 1MPa nitrogen and keeps high-pressure environment in kettle.It stirs and is raised to 120 DEG C of reaction temperature according to the rate of 5 DEG C/min.React 4h
Afterwards, stop heating, slow release nitrogen after cooling is filtered, 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 being concentrated is (containing a small amount of molten
Agent), it can be directly used for production purifying vehicle exhaust fuel oil additive.
GC-MS analysis is carried out to enriched product after reaction, the yield of confirmation form tert-butyl ferrocene is 25%, more
The yield of tert-butyl ferrocene is 5%, and the total recovery of tert-butyl 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.
Reaction kettle volume: 100ml
Ferrocene: 2g
Catalyst: 1g
Alkylating reagent: 8g
Trimethylbenzene: 20ml
Reaction temperature: 180 DEG C
Nitrogen pressure: 1MPa
Reaction time: 4h
Stirring rate: 500r/min
Reaction carries out in 100ml autoclave, and charge and discharge nitrogen is multiple before reacting, and replaces remaining air in autoclave body, and fill
Enter 1MPa nitrogen and keeps high-pressure environment in kettle.It stirs and is raised to 180 DEG C of reaction temperature according to the rate of 5 DEG C/min.React 4h
Afterwards, stop heating, slow release nitrogen after cooling is filtered, 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 being concentrated is (containing a small amount of molten
Agent), it can be directly used for production purifying vehicle exhaust fuel oil additive.
GC-MS analysis is carried out to enriched product after reaction, the yield of confirmation form tert-butyl ferrocene is 85%, more
The yield of tert-butyl ferrocene is 10%, and the total recovery of tert-butyl 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.
Reaction kettle volume: 100ml
Ferrocene: 2g
Catalyst: 1g
Alkylating reagent: 2g
Toluene: 20ml
Reaction temperature: 230 DEG C
Nitrogen pressure: 1MPa
Reaction time: 4h
Stirring rate: 500r/min
Reaction carries out in 100ml autoclave, and charge and discharge nitrogen is multiple before reacting, and replaces remaining air in autoclave body, and fill
Enter 1MPa nitrogen and keeps high-pressure environment in kettle.It stirs and is raised to 230 DEG C of reaction temperature according to the rate of 5 DEG C/min.React 4h
Afterwards, stop heating, slow release nitrogen after cooling is filtered, 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 being concentrated is (containing a small amount of molten
Agent), it can be directly used for production purifying vehicle exhaust fuel oil additive.
GC-MS analysis is carried out to enriched product after reaction, the yield of confirmation form tert-butyl ferrocene is 75%, more
The yield of tert-butyl ferrocene is 7%, and the total recovery of tert-butyl 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.
Reaction kettle volume: 100ml
Ferrocene: 2g
Catalyst: 1g
Alkylating reagent: 4g
Toluene: 20ml
Reaction temperature: 180 DEG C
Nitrogen pressure: 1MPa
Reaction time: 4h
Stirring rate: 500r/min
Reaction carries out in 100ml autoclave, and charge and discharge nitrogen is multiple before reacting, and replaces remaining air in autoclave body, and fill
Enter 1MPa nitrogen and keeps high-pressure environment in kettle.It stirs and is raised to 180 DEG C of reaction temperature according to the rate of 5 DEG C/min.React 4h
Afterwards, stop heating, slow release nitrogen after cooling is filtered, 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 being concentrated is (containing a small amount of molten
Agent), it can be directly used for production purifying vehicle exhaust fuel oil additive.
GC-MS analysis is carried out to enriched product after reaction, the yield of confirmation form ethyl dicyclopentadienyl iron is 45%, more 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, and with silica gel load alchlor (load capacity 40%) for catalyst, toluene is molten
Agent, hexene are alkylating reagent.
Reaction kettle volume: 100ml
Ferrocene: 2g
Catalyst: 1g
Alkylating reagent: 4g
Toluene: 20ml
Reaction temperature: 180 DEG C
Nitrogen pressure: 1MPa
Reaction time: 4h
Stirring rate: 500r/min
Reaction carries out in 100ml autoclave, and charge and discharge nitrogen is multiple before reacting, and replaces remaining air in autoclave body, and fill
Enter 1MPa nitrogen and keeps high-pressure environment in kettle.It stirs and is raised to 180 DEG C of reaction temperature according to the rate of 5 DEG C/min.React 4h
Afterwards, stop heating, slow release nitrogen after cooling is filtered, 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 being concentrated is (containing a small amount of molten
Agent), it can be directly used for production purifying vehicle exhaust fuel oil additive.
GC-MS analysis is carried out to enriched product after reaction, the yield of confirmation form hexyl ferrocene is 40%, mostly 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 with alumina load phosphotungstic acid (load capacity 30%) for catalyst, toluene is
Solvent, the tert-butyl alcohol are alkylating reagent.
Reaction kettle volume: 100ml
Ferrocene: 2g
Catalyst: 1g
Alkylating reagent: 4g
Toluene: 20ml
Reaction temperature: 180 DEG C
Nitrogen pressure: 1MPa
Reaction time: 4h
Stirring rate: 500r/min
Reaction carries out in 100ml autoclave, and charge and discharge nitrogen is multiple before reacting, and replaces remaining air in autoclave body, and fill
Enter 1MPa nitrogen and keeps high-pressure environment in kettle.It stirs and is raised to 180 DEG C of reaction temperature according to the rate of 5 DEG C/min.React 4h
Afterwards, stop heating, slow release nitrogen after cooling is filtered, 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 being concentrated is (containing a small amount of molten
Agent), it can be directly used for production purifying vehicle exhaust fuel oil additive.
GC-MS analysis is carried out to enriched product after reaction, the yield of confirmation form tert-butyl ferrocene is 65%, more
The yield of tert-butyl ferrocene is 22%, and the total recovery of tert-butyl ferrocene is 87%.
Embodiment 7
This example is using ferrocene as raw material, and with alumina load phosphomolybdic acid (load capacity 30%) for catalyst, toluene is
Solvent, the tert-butyl alcohol are alkylating reagent.
Reaction kettle volume: 100ml
Ferrocene: 2g
Catalyst: 1g
Alkylating reagent: 4g
Toluene: 20ml
Reaction temperature: 230 DEG C
Nitrogen pressure: 1MPa
Reaction time: 4h
Stirring rate: 500r/min
Reaction carries out in 100ml autoclave, and charge and discharge nitrogen is multiple before reacting, and replaces remaining air in autoclave body, and fill
Enter 1MPa nitrogen and keeps high-pressure environment in kettle.It stirs and is raised to 230 DEG C of reaction temperature according to the rate of 5 DEG C/min.React 4h
Afterwards, stop heating, slow release nitrogen after cooling is filtered, 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 being concentrated is (containing a small amount of molten
Agent), it can be directly used for production purifying vehicle exhaust fuel oil additive.
GC-MS analysis is carried out to enriched product after reaction, the yield of confirmation form tert-butyl ferrocene is 65%, more
The yield of tert-butyl ferrocene is 21%, and the total recovery of tert-butyl ferrocene is 86%.
Target product total recovery such as the following table 1 of 1-7 of the embodiment of the present invention:
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 more alkylation ferrocene derivatives, the monoalkylation ferrocene derivatives are the rings penta in ferrocene
There are the ferrocene derivatives of 1 substitution alkyl on dialkylene, more alkylation ferrocene derivatives are the rings penta in ferrocene
There are the ferrocene derivatives of 2~3 substitution alkyl on dialkylene；The monoalkylation ferrocene derivatives are two cyclopentadienyl of tert-butyl
Iron, more alkylation ferrocene derivatives are more tert-butyl ferrocene；It is characterized in that the method are as follows:
It takes ferrocene, alkylating reagent, organic solvent to mix with load-type solid acid catalyst to be added in autoclave, room temperature
Under be filled with nitrogen to 0.5~2.5MPa, airtight heating is to 80 DEG C~250 DEG C, and the reaction was stirred for 2 to 6 hours；That reaction was completed is mixed for reaction
It closes liquid filtering, filtrate decompression distillation and concentration, alkylation ferrocene derivatives is made；
The alkylating reagent is isobutene,
The ratio between amount of substance of the ferrocene, alkylating reagent is 1:1~13；
The load-type solid acid catalyst is made of carrier and the acid catalyst that is carried on carrier, and load capacity is 25~
75%, the acid catalyst is phosphoric acid；The carrier is silica gel.
2. the method as described in claim 1, it is characterised in that the ratio between the ferrocene, amount of substance 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 the 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 the 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 distillation is evaporated under reduced pressure at a temperature of 80 DEG C, is removed
Solvent and unreacted raw material are removed, target product is made and is alkylated ferrocene derivatives.
7. the method as described in claim 1, it is characterised in that the temperature of the reaction is 120~230 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710312200.4A CN107011390B (en) | 2014-09-30 | 2014-09-30 | A kind of synthetic method being alkylated ferrocene derivatives |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410521342.8A CN104262410B (en) | 2014-09-30 | 2014-09-30 | A kind of synthetic method for being alkylated ferrocene derivatives |
| CN201710312200.4A CN107011390B (en) | 2014-09-30 | 2014-09-30 | A kind of synthetic method being alkylated ferrocene derivatives |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410521342.8A Division CN104262410B (en) | 2014-09-30 | 2014-09-30 | A kind of synthetic method for being alkylated ferrocene derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107011390A CN107011390A (en) | 2017-08-04 |
| CN107011390B true CN107011390B (en) | 2019-10-18 |
Family
ID=52154018
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410521342.8A Active CN104262410B (en) | 2014-09-30 | 2014-09-30 | A kind of synthetic method for being alkylated ferrocene derivatives |
| CN201710312200.4A Active CN107011390B (en) | 2014-09-30 | 2014-09-30 | A kind of synthetic method being alkylated ferrocene derivatives |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410521342.8A Active CN104262410B (en) | 2014-09-30 | 2014-09-30 | A kind of synthetic method for being alkylated ferrocene derivatives |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN104262410B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111154519A (en) * | 2020-01-09 | 2020-05-15 | 上海鸣马新能源科技有限公司 | Gasoline-saving agent |
| CN116854748B (en) * | 2023-05-10 | 2023-12-19 | 研峰科技(北京)有限公司 | Synthesis process of diethyl cyclopentadienyl iron |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945445A (en) * | 2015-06-01 | 2015-09-30 | 嘉兴市正大化工有限公司 | Production method of ethylferrocene |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101037452B (en) * | 2007-03-27 | 2011-05-11 | 武汉大学 | Method for preparing acyl Ferrocene |
| CN101456882B (en) * | 2007-12-14 | 2011-04-06 | 中国中化股份有限公司 | Acylated ferrocene solid phase synthesis method |
-
2014
- 2014-09-30 CN CN201410521342.8A patent/CN104262410B/en active Active
- 2014-09-30 CN CN201710312200.4A patent/CN107011390B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104945445A (en) * | 2015-06-01 | 2015-09-30 | 嘉兴市正大化工有限公司 | Production method of ethylferrocene |
Non-Patent Citations (1)
| Title |
|---|
| 叔丁基二茂铁的合成及其应用;张帆，;《辽宁化工》;19881231;第17-21页，尤其是第19页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262410A (en) | 2015-01-07 |
| CN107011390A (en) | 2017-08-04 |
| CN104262410B (en) | 2017-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Phan et al. | Towards applications of metal–organic frameworks in catalysis: C–H direct activation of benzoxazole with aryl boronic acids using Ni 2 (BDC) 2 (DABCO) as an efficient heterogeneous catalyst | |
| US7049266B2 (en) | Layered double hydroxides supported nanopalladium catalysts for Heck-, Suzuki, Sonogashira-, and Stille type coupling reactions of haloarenes | |
| CN101306383B (en) | Chiral organic micromolecule catalyst loaded by heteropoly acid and preparation method and use thereof | |
| Forkel et al. | Lanthanide replacement in organic synthesis: Luche-type reduction of α, β-unsaturated ketones in the presence of calcium triflate | |
| CN103402958B (en) | The preparation method of dibasic alcohol list tertbutyl ether compound | |
| CN107011390B (en) | A kind of synthetic method being alkylated ferrocene derivatives | |
| CN101633594B (en) | Environmental-friendly Friedel-Crafts reaction postprocessing method | |
| Lee et al. | Palladium-catalyzed cross-coupling of (hetero) aryl or alkenyl sulfonates with aryl titanium as the multi-functional reagent | |
| CN1966476A (en) | Iron-catalysed allylic alkylation | |
| CN103408414B (en) | Preparation method of 2-hydroxyl-4-substituted arone compound | |
| CN103204766B (en) | Method for separating and purifying m-cresol from mixture of m-cresol and p-cresol | |
| CN100406417C (en) | Method for preparing 1,1,1,3,3 - pentachlorobutane from materials of chloropropene and carbon tetrachloride under tempering and polymerizing catalyst | |
| CN110079359B (en) | Preparation method of alkylated gasoline | |
| Fu et al. | Vapor-phase highly selective O-methylation of catechol with methanol over ZnCl2 modified γ-Al2O3 catalysts | |
| CN101786016B (en) | Preparation method and application method of novel immobilized Lewis acid catalyst | |
| CN105218466A (en) | A kind of preparation method of 2,4,6-tri-(2 ', 4 '-dihydroxy phenyl)-1,3,5-triazines | |
| CN103012276A (en) | Long-chain alkyl sulfoacid functionalized heteropolyacid salt, preparation method and application of long-chain alkyl sulfoacid functionalized heteropolyacid salt | |
| CN102617644A (en) | Synthesizing and refining method of flame retardant intermediate DOPO | |
| WO2011020900A2 (en) | A process for preparing biaryl compounds in a suzuki type reaction allowing product isolation and catalyst recycling in one step | |
| EP1464394A1 (en) | Supported nanopalladium catalyst for C-C coupling reactions of haloarenes | |
| Bhunia et al. | Heterogeneous Stille and Sonogashira cross-coupling reactions over palladium anchored mesoporous silica catalyst | |
| CN101857579B (en) | Synthesis method of 2-amino-5,6-dichlorobenzothiazole | |
| CN100497286C (en) | Preparation method of 2,3-bihydrogen-1-indenone and its derivative | |
| JP2013177353A (en) | Method for producing carboxylic acid ester | |
| Hubert et al. | Ruthenium-catalyzed allylation reaction in ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |