CN1101400C - Preparation method of ferrocenyl formyl compound - Google Patents
Preparation method of ferrocenyl formyl compound Download PDFInfo
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- CN1101400C CN1101400C CN00102500A CN00102500A CN1101400C CN 1101400 C CN1101400 C CN 1101400C CN 00102500 A CN00102500 A CN 00102500A CN 00102500 A CN00102500 A CN 00102500A CN 1101400 C CN1101400 C CN 1101400C
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- ferrocenyl
- ferrocene
- ferrocenyl formyl
- formyl compound
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Abstract
The present invention relates to a preparation method of a ferrocenyl formyl compound, which comprises: ferrocene or derivatives thereof, organic alkali and an organic solvent are put in a reaction bottle, at the temperature of sub 30 to 60 DEG C and under the protection of inert gas and stirring, solid phosgene is added, and the mixture is stirred for 8 to 14 hr; products are filtered by suction, filtrates are evaporated to dryness, residues are dissolved by using an organic solvent, and filtrates are concentrated and settled at room temperature to obtain a crystal product. The ferrocenyl formyl compound prepared by the present invention has high yield, simple experiment operation, convenient post-treatment and no generation of black impurities.
Description
The present invention relates to the preparation of ferrocenyl formyl compound.
The ferrocene acyl chlorides is a kind of important synthesis intermediates, and that its derivative shows is antitumor, desinsection, sterilization and plant growth regulating activity.Ferrocenyl is a good aromatic group of hydrophobicity, alternative phenyl ring in some medicines or pesticide molecule and still keep biological activity.Make raw material as rom Haars Co., Ltd with the ferrocene acyl chlorides phenyl ring in the bishydrazide molecule is replaced with ferrocene, obtain containing the bishydrazide compound of ferrocenyl, show very high insect growth regulator activity.On the other hand, ferrocenyl has two rotatable copline cyclopentadienyls and unique redox characteristic, therefore the ferrocene carbonyl is incorporated in supramolecule and the molecular element as raw material with the ferrocene acyl chlorides recently, ferrocenyl itself is to form supramolecular organometallic skeletal as molecular receptor with the peptide chain that contains ferrocenyl.
Bibliographical information ferrocene acyl chlorides is to react by ferrocenecarboxylic acid and suitable chlorination reagent to make, used chlorination reagent has: phosphorus pentachloride (D.W.Mayo, P.D.Shaw, M.Rausch, Chem.and Ind. (London) (1957) 1388.), phosphorus trichloride (W.Ji-Tao, Z.Yun-Wen, X.Yu-Min, et al, Chem.J.Chinese Univ.14 (1993) 801.), oxalyl chloride (H.Falk, C.Krasa, K.Schlogl, Monat.Chem.100 (1969) 1552.) and thionyl chloride (H.J.Lorkowski, R.Pannier, A.Wende, J.Prakt.Chem.35 (1967) 149.).Ferrocenecarboxylic acid can prepare with following several method: the acetylize of (1) ferrocene elder generation; obtain ferrocenecarboxylic acid with hypochlorite or iodine oxidation again; but oxidization-hydrogenation ratio too low (14%-47.8%); (2) ferrocene elder generation formylation; obtain ferrocenecarboxylic acid (G.Schmitt with silver suboxide or Manganse Dioxide oxidation again; S.Ozman; J.Org.Chem.41 (1976) 3331.); same oxidization-hydrogenation ratio is too low; (3) ferrocene becomes lithium salts with butyllithium; obtain ferrocenecarboxylic acid (D.W.Mayo with carbon dioxide reaction again; P.D.Shaw; M.Rausch; Chem.andInd. (London) (1957) 1388.); total recovery has only 37%; and operate too numerous and diverse; (4) after ferrocene and o-chlorobenzoyl chloride are carried out the Friedel-Crafts acylation reaction; the spent glycol dme is made solvent again; obtain ferrocenecarboxylic acid (E.R.Biehl with tertiary butyl nak response; P.C.Reeves; Synthesis 6 (1973) 360.); though the total recovery of this reaction can reach 88%; but it is too expensive that used o-chlorobenzoyl chloride and tertiary butyl potassium are made raw material; (5) hydrolysis of cyano group ferrocene can obtain ferrocenecarboxylic acid (A.N.Nesmeyanov; E.G.Perevalova; L.P.Yureva, etal, Izv.Akad.Nauk SSSR; Ser.Khim.; (1963) 1377.), the yield of this reaction is 69%, but raw material cyano group ferrocene is too expensive; (6) hydrolysis of ferrocene bamic acid methyl esters also can obtain ferrocenecarboxylic acid (D.E.Bublitz; G.H.Harris, J.Organomet.Chem., 4 (1965) 404.); the yield of this reaction is 70%, gets but raw material ferrocene bamic acid methyl esters is bad.Six kinds of methods of above-mentioned bibliographical information are owing to synthetic difficulty causes ferrocenecarboxylic acid very expensive.And, can produce a large amount of black impurities when ferrocenecarboxylic acid and phosphorus pentachloride, phosphorus trichloride, oxalyl chloride and thionyl chloride prepared in reaction ferrocene acyl chlorides, and yield is low.
Di-ferrocene ketone is a kind of stable combustion modifications thing, and the rocket fuel that it makes with organic high poly-fuel and ammoniumper chlorate can significantly increase the combustionvelocity of fuel.Di-ferrocene ketone is because insensitive to water and hexanaphthene, so the mixture of it and nitric acid preparation can be used as high temperature percussion primer, electronic detonator, detonator and priming charge.The still synthetic various hydrazones of di-ferrocene ketone, sulfo-, seleno, telluro di-ferrocene ketone, the important intermediate of four ferrocenyl ethene etc., simultaneously di-ferrocene ketone since two luxuriant rings with a sp
2The carbon of hydridization connects and causes it and be raw material and the synthetic product has unique redox characteristic with it.Document reacts to synthesize di-ferrocene ketone with ferrocene again with the earlier synthetic ferrocene acyl chlorides of ferrocenecarboxylic acid, and its total recovery only has 38% (A.F.Ellis, C.J.Michejda, et al, J.Am.Chem.Soc.82 (1960) 4112. for K.L.Rinehart, Jr.).
Up to now, still find no the processing method that ideal prepares above-mentioned ferrocenyl formyl compound.
The preparation method who the purpose of this invention is to provide a kind of ferrocenyl formyl compound, outstanding feature of the present invention select for use solid phosgene directly to make raw material with the ferrocene that cheaply is easy to get, and experimental implementation is simple, convenient post-treatment.The present invention can overcome the deficiencies in the prior art, its yield is higher than the yield of ferrocenecarboxylic acid and phosphorus pentachloride, phosphorus trichloride, oxalyl chloride or thionyl chloride reaction, do not produce black impurity, on experimental implementation and yield, all be far superior to currently known methods, and avoided the preparation of ferrocenecarboxylic acid.
The present invention adopts following reaction:
The present invention is reflected at-30 to+60 ℃ at this, carries out in preferred-15 to+20 ℃ the temperature range.Ferrocene or its derivative, organic bases and organic solvent are placed reaction flask, stir down, the noble gas protection, (reactant molar ratio is 3: 1-3), stir 8-14hr to add solid phosgene; Suction filtration, filtrate evaporated under reduced pressure is extremely done, the residue organic solvent dissolution, suction filtration, filtrate decompression concentrates, and places under the room temperature, obtains crystalline product, filters, dry getting final product.
Concrete preparation method of the present invention can select for use solid phosgene and ferrocene direct reaction to prepare the ferrocene acyl chlorides, the suitable solvent of this reaction is tetrahydrofuran (THF), ether, toluene, benzene, ethyl acetate, chloroform, methylene dichloride or 1,2-ethylene dichloride and their mixing, best solvent are methylene dichloride; Suitable alkali is organic bases, for example Trimethylamine 99, triethylamine, pyridine, N-methylamino pyridine or N, N dimethylamine yl pyridines; The mol ratio of said ferrocene and solid phosgene is 3: 1-3; This is reflected at-30 to+60 ℃, carries out in preferred-15 to+20 ℃ the temperature range; This reaction process is as follows:
Needed solid phosgene prepares with currently known methods in the reaction.
The present invention can select solid phosgene and ferrocenecarboxylic acid prepared in reaction for use ferrocene acyl chlorides, the suitable solvent of this reaction is tetrahydrofuran (THF), ether, toluene, benzene, ethyl acetate, chloroform, methylene dichloride or 1, the 2-ethylene dichloride.Best solvent is a methylene dichloride; Suitable alkali is organic bases, for example Trimethylamine 99, triethylamine, pyridine, N-methylamino pyridine or N, N dimethylamine yl pyridines or their mixing.This is reflected at-30 to+60 ℃, carries out in preferred-15 to+20 ℃ the temperature range.
The present invention also can prepare di-ferrocene ketone with solid phosgene and ferrocene single step reaction, and suitable solvent is tetrahydrofuran (THF), ether, toluene, benzene, ethyl acetate, chloroform, methylene dichloride or 1, the 2-ethylene dichloride.Best solvent is a methylene dichloride.Suitable alkali is organic bases, for example Trimethylamine 99, triethylamine, pyridine, N-methylamino pyridine or N, N dimethylamine yl pyridines.This is reflected at-30 to+60 ℃, carries out in preferred-15 to+20 ℃ the temperature range.This reaction needed is carried out in the presence of lewis acid, and the suitable lewis acid of this reaction has: aluminum chloride, zinc dichloride or tin tetrachloride etc., preferred aluminum trichloride (anhydrous).
Embodiment:
Solid phosgene and ferrocene prepared in reaction ferrocene acyl chlorides
With the triethylamine (6mmol) and the 15mL 1 of ferrocene (5.4mmol), heavily steaming, the 2-ethylene dichloride places reaction flask under 0 ℃, under the ice bath cooling and stirring, and logical nitrogen protection.Drip the 15mL1 of solid phosgene (2mmol) then, the solution of 2-ethylene dichloride.After adding, 0 ℃ is continued to stir 2hr, stirring at room 12hr down.Suction filtration, filtrate evaporated under reduced pressure adds normal hexane and is heated to dissolving to doing in the residue, suction filtration, filtrate decompression concentrates, and place crystallization and get red crystalline product (0.51g, yield are 38.1%), mp 49-51 ℃ (literature value,
7Mp=49 ℃);
1H NMR (CDCl
3) δ 4.32 (s, 5H, C
5H
5), 4.63 (s, 2H, C
5H
4), 4.91 (s, 2H, C
5H
4).
Solid phosgene and ferrocenecarboxylic acid prepared in reaction ferrocene acyl chlorides
Under nitrogen protection; the triethylamine (3.29mmol) and the N that with ferrocenecarboxylic acid (3.13mmol), heavily steam under 0 ℃, the 10mL dichloromethane solution of N dimethylamine yl pyridines (1.65mmol) drop in the 30mL dichloromethane solution of solid phosgene (3.29mmol) of stirring.After adding, 0 ℃ is continued to stir 1hr, stirring at room 11hr down.Suction filtration, filtrate evaporated under reduced pressure adds normal hexane and is heated to dissolving to doing in the residue, suction filtration, filtrate decompression concentrates, and place crystallization and get red crystalline product (0.48g, yield are 61.5%), mp 49-51 ℃ (literature value,
7Mp=49 ℃);
1HNMR (CDCl
3) δ 4.32 (s, 5H, C
5H
5), 4.63 (s, 2H, C
5H
4), 4.91 (s, 2H, C
5H
4).
Synthesizing of di-ferrocene ketone:
Under nitrogen protection, under-15 ℃, the 10mL dichloromethane solution of solid phosgene (1.61mmol) and the triethylamine (4.83mmol) that heavily steams are added drop-wise to simultaneously the 30mL dichloromethane solution of ferrocene (8.06mmol) and aluminum trichloride (anhydrous) (8.06mmol) from different funnels.After adding ,-15 ℃ are continued to stir 2hr, stirring at room 6hr down.Reaction mixture is poured in the frozen water, uses dichloromethane extraction, the organic phase anhydrous magnesium sulfate drying, suction filtration, filtrate evaporated under reduced pressure is to doing, and residue is crossed chromatographic column, products therefrom gets red needle-like crystal product (0.81g, yield are 50.6%) with the Virahol recrystallization; Mp 203-204 ℃ (literature value,
15Mp=204 ℃); IR (KBr) 3113.5,1607.1,1462.4,1382.4,1291.6,1102.0,1059.6,804.6,490.3cm
-1 1H NMR (CDCl
3) δ 4.23 (s, 5H, C
5H
5), 4.54 (s, 2H, C
5H
4), 5.02 (s, 2H, C
5H
4) .C
21H
18OFe
2, analytical calculation value: C, 63.36; H, 4.56. experimental value: C, 63.16; H, 4.28.
Claims (8)
1. the preparation method of a ferrocenyl formyl compound is characterized in that it makes through following reaction:
R=H or-CO
2H;
Its concrete preparation process is:
Ferrocene or its derivative, organic bases and organic solvent are placed reaction flask, and under-30 to+60 ℃ of temperature, noble gas protection and stirring add solid phosgene down, stir 8-14hr; Suction filtration, filtrate evaporated under reduced pressure is extremely done, the residue organic solvent dissolution, suction filtration, filtrate decompression concentrates, and places under the room temperature, obtains crystalline product, and product is filtered, dry getting final product.
2. according to the preparation method of the said ferrocenyl formyl compound of claim 1, the mol ratio that it is characterized in that said ferrocene or its derivative and solid phosgene is 3: 1-3.
3. according to the preparation method of the said ferrocenyl formyl compound of claim 1, it is characterized in that said organic bases is Trimethylamine 99, triethylamine, pyridine, N-methylamino pyridine or N, the N dimethylamine yl pyridines.
4. according to the preparation method of said 1 ferrocenyl formyl compound of claim; it is characterized in that said organic solvent is tetrahydrofuran (THF), ether, toluene, benzene, ethyl acetate, chloroform, methylene dichloride or 1; 2-ethylene dichloride, best solvent are methylene dichloride or 1, the 2-ethylene dichloride.
5. according to the preparation method of said 1 ferrocenyl formyl compound of claim, it is characterized in that said temperature of reaction is to carry out in-15 to+20 ℃ temperature range.
6. according to the preparation method of said 5 ferrocenyl formyl compounds of claim, it is characterized in that said temperature of reaction is to carry out under 0 ℃ temperature.
7. according to the preparation method of said 3 ferrocenyl formyl compounds of claim, it is characterized in that said organic bases is triethylamine and N, the N dimethylamine yl pyridines.
8. according to the preparation method of said 1 ferrocenyl formyl compound of claim, when it is characterized in that said ferrocenyl formyl compound product R ', add aluminum chloride, zinc dichloride or tin tetrachloride, preferred aluminum chloride for ferrocenyl formyl.
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|---|---|---|---|
| CN00102500A CN1101400C (en) | 2000-03-15 | 2000-03-15 | Preparation method of ferrocenyl formyl compound |
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| CN102002071B (en) * | 2010-10-21 | 2013-06-12 | 聊城大学 | Ferrocenedicarboxylic acid trialkyl tin chloride coordination compound as well as preparation method and application thereof |
| CN104788503B (en) * | 2015-04-13 | 2017-08-08 | 桂林医学院 | Ferroquine promise keto acyl aminated compounds and its preparation method and application |
| WO2019036633A1 (en) * | 2017-08-17 | 2019-02-21 | The Trustees Of Columbia University In The City Of New York | Redox flow batteries and compounds for battery application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158621A (en) * | 1994-07-13 | 1997-09-03 | 柏林弗赖恩大学诊断研究学院有限公司 | Complexes for use in the diagnosis of vascular diseases |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158621A (en) * | 1994-07-13 | 1997-09-03 | 柏林弗赖恩大学诊断研究学院有限公司 | Complexes for use in the diagnosis of vascular diseases |
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