CN1775788A - Method for synthesizing acyl ferrocene - Google Patents
Method for synthesizing acyl ferrocene Download PDFInfo
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- CN1775788A CN1775788A CN 200510019956 CN200510019956A CN1775788A CN 1775788 A CN1775788 A CN 1775788A CN 200510019956 CN200510019956 CN 200510019956 CN 200510019956 A CN200510019956 A CN 200510019956A CN 1775788 A CN1775788 A CN 1775788A
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Abstract
The invention discloses a method for synthesizing acyl ferrocene, mainly using acid anhydride as acylating reagent, and boron trifluoride ethyl ether as catalyst, reacting 3-4 hours at normal temperature. The invention overcomes the defects of the existing method, and remarkably raises the yield and does not generate disubstitution products; and the dosage of acid anhydride is less, only needing exceed by 5% and the invention can obtain high purity products of higher melting point acyl ferrocene such as acetyl ferrocene without column chromatographic resolution.
Description
Technical field
The present invention relates to a kind of method of synthesizing acyl ferrocene, particularly a kind of method that adopts ferrocene and acid anhydrides synthesizing acyl ferrocene.
Background technology
Ferrocene group has aromaticity, oxidation-reduction quality and hypotoxicity, and its derivative has a wide range of applications in fields such as polymkeric substance, electrochemistry, medical science.Ferrocene group is introduced different molecules, new in the hope of obtaining, or the compound with property is a focus of ferrocene chemical research in recent years.Because the acyl group that acyl Ferrocene contained is a very active group of chemical property, therefore be the important intermediate of synthetic ferrocene deriv.
The synthetic employing of acyl Ferrocene paid-the Ke acylation reaction more, and acylting agent commonly used has acid anhydrides, acyl chlorides, carboxylic acid etc., and catalyst system therefor is a Lewis acid, as phosphoric acid, aluminum trichloride (anhydrous) etc.Li Baoguo etc. are published in " acetylferrocene synthetic " literary composition on fifth phase calendar year 2001 " chemical reagent ", make catalyzer with aluminum chloride, and Acetyl Chloride 98Min. is an acylting agent, the synthesis of acetyl ferrocene, and through column chromatography for separation, productive rate 81.6%.And produce a spot of diacetyl ferrocene.Tang Jie etc. are published in " intersect the synthetic ferrocene diarylethene derivatives of hydroxyl reductive coupling method " literary composition on the first phase in 1999 " synthetic chemistry ", with excessive fortyfold approximately propionic anhydride and ferrocene reaction, phosphoric acid does catalyst with 85%, the synthesizing propionyl ferrocene, column chromatography for separation, productive rate 80.5% has two substitution products equally.Present stage acyl Ferrocene synthetic all adopt aforesaid method basically, and all there is the common defective in aforesaid method: the one, productive rate is not high, the 2nd, two substitution products are arranged, the 3rd, need use column chromatography just and can reach certain purity.
Summary of the invention
The purpose of this invention is to provide that a kind of method is easy, productive rate is high, the method for the purified synthesizing acyl ferrocene of product.
The object of the present invention is achieved like this: a kind of method of synthesizing acyl ferrocene; mol ratio in 1.00: 1.05 in reactor adds ferrocene and acid anhydrides; use organic solvent dissolution; be cooled to-1～5 ℃; add boron trifluoride ether solution under stirring and make catalyzer; boron trifluoride diethyl etherate is 2: 1 with the mol ratio of ferrocene; keep temperature to continue to stir 1 hour, stirring reaction joins reaction mixture in 0～5 ℃ the excessive acetic acid saturated aqueous solution of sodium to fully under the room temperature; standing demix; tell organic phase, the water organic solvent extraction merges organic phase; water successively; the saturated sodium bicarbonate washing is to alkalescence; wash organic phase again with water for neutral, add the siccative drying, filter; the sherwood oil that in filtrate, adds 90～120 ℃; behind the vacuum concentration, crystallisation by cooling filters; the filter cake petroleum ether obtains highly purified acyl Ferrocene crystal.
The excessive acetic acid saturated aqueous solution of sodium temperature that adds is 0 ℃.90～120 ℃ of sherwood oil volumes that in filtrate, add be filtrate volume half.The volume of material is for concentrating 1/3 of front volume behind the vacuum concentration.
The method of synthesizing acyl ferrocene provided by the invention is an acylting agent with the acid anhydrides, and boron trifluoride diethyl etherate is a catalyzer, reacts synthesizing acyl ferrocene at normal temperatures, and productive rate is significantly improved; There are not two substitution products; The acid anhydrides consumption is few, only needs excessive 5%; To the higher acyl Ferrocene of fusing point such as acetylferrocene not the demand pole chromatographic separation just can obtain highly purified product.
Embodiment
[example 1]: in clean, exsiccant reactor, add 3.72Kg (20mol) ferrocene and 2.1L (21mol) diacetyl oxide, dissolve with the 15L methylene dichloride, be cooled to 0 ℃, stir the mixing solutions that slowly adds 6L boron trifluoride diethyl etherate and 10L methylene dichloride down, continue to stir 1 hour, stirred 4 hours under the room temperature, to reacting completely.Reaction mixture joined in batches in 0 ℃ the excessive acetic acid saturated aqueous solution of sodium, standing demix is told organic phase, and water is with twice of 15L dichloromethane extraction.Merge organic phase, extremely alkalescence, deionized water washing are to neutral with 10L deionized water, the washing of 10L saturated sodium bicarbonate solution successively, and adding anhydrous magnesium sulfate drying 4 hours filters.Add the sherwood oil of 30L90～120 ℃ to filtrate, be concentrated into 30L, crystallisation by cooling filters, and a small amount of petroleum ether of filter cake obtains orange-yellow tabular crystal 4.00Kg, productive rate 87.72%, mp84.0-85.0 ℃.
[example 2]: in clean, exsiccant reactor, add 7.44Kg (40mol) ferrocene and 4.1L (41mol) diacetyl oxide, dissolve with the 25L methylene dichloride, be cooled to 4 ℃, stir the mixing solutions that slowly adds 12L boron trifluoride diethyl etherate and 20L methylene dichloride down, continue to stir 1 hour, stirred 2 hours under the room temperature.Reaction mixture joined in batches in 4 ℃ the excessive acetic acid saturated aqueous solution of sodium, standing demix is told organic phase, and water is with twice of 30L dichloromethane extraction.Merge organic phase, extremely alkalescence, deionized water washing are to neutral with 20L deionized water, the washing of 20L saturated sodium bicarbonate solution successively, and adding anhydrous magnesium sulfate drying 4 hours filters.Add the sherwood oil of 60L90～120 ℃ to filtrate, be concentrated into 60L, crystallisation by cooling filters, and a small amount of petroleum ether of filter cake obtains orange-yellow tabular crystal 7.80Kg, productive rate 85.53%, mp84.0-85.0 ℃.
[example 3]: the reflux condensing tube of mounting strap calcium chloride tube on 125mL exsiccant round-bottomed flask, built-in 3.72g (0.020mol) ferrocene with the dissolving of 15mL methylene dichloride, adds 3.0mL (0.021mol) propionic anhydride.Induction stirring under ice bath cooling splashes into the mixing solutions of 6mL boron trifluoride diethyl etherate and 10mL methylene dichloride with constant pressure funnel, continues to stir 1h, stirs 3h under the room temperature.The ice bath cooling adds excessive sodium acetate saturated aqueous solution down, changes in the separating funnel, and standing demix is told organic phase, and water merges organic phase with twice of dichloromethane extraction (10mL * 2).Water, saturated sodium bicarbonate solution washing are to alkalescence successively, water washing (each 10mL * 2), be neutral to the pH detection paper, anhydrous magnesium sulfate drying filters, and rotary evaporation goes out a large amount of methylene dichloride, add the absorption of 10.0g chromatographic silica gel, column chromatography for separation obtains orange-yellow tabular crystal 4.31g, productive rate 89.05%, mp30.0-30.5 ℃.(because propionyl ferrocene fusing point is low, non-crystallizable in solvent, must adopt column chromatography for separation).
Claims (4)
1; a kind of method of synthesizing acyl ferrocene; it is characterized in that: the mol ratio in 1.00: 1.05 in reactor adds ferrocene and acid anhydrides; use organic solvent dissolution; be cooled to-1～5 ℃; add boron trifluoride ether solution under stirring and make catalyzer; boron trifluoride diethyl etherate is 2: 1 with the mol ratio of ferrocene; keep temperature to continue to stir 1 hour, stirring reaction joins reaction mixture in 0～5 ℃ the excessive acetic acid saturated aqueous solution of sodium to fully under the room temperature; standing demix; tell organic phase, the water organic solvent extraction merges organic phase; water successively; the saturated sodium bicarbonate washing is to alkalescence; wash organic phase again with water for neutral, add the siccative drying, filter; the sherwood oil that in filtrate, adds 90～120 ℃; behind the vacuum concentration, crystallisation by cooling filters; the filter cake petroleum ether obtains highly purified acyl Ferrocene crystal.
2, the method for synthesizing acyl ferrocene according to claim 1 is characterized in that: the excessive acetic acid saturated aqueous solution of sodium temperature of adding is 0 ℃.
3, the method for synthesizing acyl ferrocene according to claim 2 is characterized in that: 90～120 ℃ of sherwood oil volumes that in filtrate, add be filtrate volume half.
4, according to the method for claim 1 or 2 or 3 described synthesizing acyl ferrocenes, it is characterized in that: the volume of material is for concentrating 1/3 of front volume behind the vacuum concentration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100199567A CN100443492C (en) | 2005-12-06 | 2005-12-06 | Method for synthesizing acyl ferrocene |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100199567A CN100443492C (en) | 2005-12-06 | 2005-12-06 | Method for synthesizing acyl ferrocene |
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| Publication Number | Publication Date |
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| CN1775788A true CN1775788A (en) | 2006-05-24 |
| CN100443492C CN100443492C (en) | 2008-12-17 |
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| CNB2005100199567A Expired - Fee Related CN100443492C (en) | 2005-12-06 | 2005-12-06 | Method for synthesizing acyl ferrocene |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456882B (en) * | 2007-12-14 | 2011-04-06 | 中国中化股份有限公司 | Acylated ferrocene solid phase synthesis method |
| CN101037452B (en) * | 2007-03-27 | 2011-05-11 | 武汉大学 | Method for preparing acyl Ferrocene |
| CN101587089B (en) * | 2008-05-23 | 2012-11-28 | 中国科学院大连化学物理研究所 | Ferrocene-porous metal-organic framework compound composite material, preparation method and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001074832A1 (en) * | 2000-03-31 | 2001-10-11 | Council Of Scientific And Industrial Research | An improved process for the preparation of acylferrocenes |
| US6239302B1 (en) * | 2000-04-07 | 2001-05-29 | Council Of Scientific & Industrial Research | Process for the preparation of acylferrocenes |
-
2005
- 2005-12-06 CN CNB2005100199567A patent/CN100443492C/en not_active Expired - Fee Related
Cited By (3)
| 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 |
| CN101587089B (en) * | 2008-05-23 | 2012-11-28 | 中国科学院大连化学物理研究所 | Ferrocene-porous metal-organic framework compound composite material, preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN100443492C (en) | 2008-12-17 |
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Granted publication date: 20081217 Termination date: 20111206 |