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Polymethylene-bridged ferrocenyl bipyrazole and synthetic method thereof

A technology of methylene bridged ferrocenyl bispyrazoles and synthetic methods, which is applied in the fields of chemical instruments and methods, metallocenes, organic chemistry, etc., and can solve the problem of inability to synthesize ferrocenyl bispyrazoles and the efficiency of synthetic methods No high-level problems, to achieve the effect of excellent target product yield, high target product yield, cheap and easy-to-obtain raw materials

Inactive Publication Date: 2009-12-30
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the synthesis method is not efficient, and the reported examples are limited to one methylene-bridged ferrocenyl bispyrazole, and cannot synthesize ferrocenyl bispyrazoles with longer bridged carbon chains.

Method used

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  • Polymethylene-bridged ferrocenyl bipyrazole and synthetic method thereof
  • Polymethylene-bridged ferrocenyl bipyrazole and synthetic method thereof
  • Polymethylene-bridged ferrocenyl bipyrazole and synthetic method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Example 1: Synthesis of 1,1'-ferrocenedimethanol 2

[0035] In a 250mL branched flask, N 2 Replaced three times, dissolved ferrocene (5.0g, 26.9mmol) in 80mL of anhydrous ether, treated with n-butyl lithium (2.5 Minhexane, 22.4mL, 56.0mmol) at room temperature, reacted at room temperature for 2h, then added TMEDA dropwise (3.2g, 27.5mmol), stirred at room temperature for 24h. Paraformaldehyde (2.0 g, 66.6 mmol) was added in batches, stirred at room temperature for 24 h, cooled to 0 °C, quenched with 50 mL of saturated aqueous ammonium chloride, extracted with 200 mL of dichloromethane, and dried with anhydrous magnesium sulfate. Filtration, concentration under reduced pressure, separation and purification by column chromatography, the chromatographic column is a silica gel column, the eluent is petroleum jelly (60-90°C) / ethyl acetate (v / v, 1:1), and the orange-yellow component is collected 2. The target product yield is 41%.

Embodiment 2

[0036] Example 2: Synthesis of 1,1'-bis(1-phenyl-3-methyl-1,3-butanedione)ferrocene 3b

[0037] In a 25mL branched flask, N 2 Replaced three times, added ferrocenyl diol compound 2 (1.00g, 4.06mmol) and benzoylacetone (1.32g, 8.12mmol), then added 2.0mL dichloromethane to dissolve it, and dissolved 1.0mL 40% hydrofluoric Acid (28.5mmol) was added dropwise, reacted at room temperature for 30min, and then diluted with 100mL ether. The organic phase was washed with 5×50 mL of water, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and dried in vacuo to obtain orange-yellow oil 3b with a yield of 79%.

Embodiment 3

[0038] Example 3: Synthesis of 1,1'-bis(3-methyl-4-methyl-5-phenylpyrazole)ferrocene 4b

[0039] In a 50mL branched flask, N 2 Replaced three times, dissolved ferrocenylbis(1,3-diketone) 3b (1.50g, 2.70mmol) in 40mL of absolute ethanol, added 85% hydrazine hydrate (2.0mL, 34.0mmol), stirred at reflux for 3h, Cool to room temperature, concentrate under reduced pressure, and then separate and purify by column chromatography. The chromatographic column is a silica gel column, and the eluent is petroleum jelly (60-90 ℃) / ethyl acetate (v / v, 1:1). Component 4b, the yield is 90%.

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Abstract

The invention discloses polymethylene-bridged ferrocenyl bipyrazole (a general formula is Fc-[(CH2)n-R1R2PzH]2, wherein Fc is 1,1'-ferrocenyl; n is between 1 and 3; R1R2 is 3,5-disubstituent; and Pz is 4-pyrazolyl) and a synthetic method thereof. Bipyrazole Fc-[(CH2)n-R1R2PzH]2 that n is equal 1 and R1 and R2 are different substituents is obtained by taking ferrocene as an initial raw material through a methylation, alkylation and condensation three-step reaction; and the synthesis of ferrocenyl-bis(4-methylene-3,5-dimethylpyrazole) that n is equal 1 and R1 is equal to R2 and is equal to methyl by utilizing a literature report method needs a five-step reaction. The method is utilized to take 1,3-diketone as a raw material to synthesize bipyrazole Fc-[(CH2)n-R1R2PzH]2 that n is equal to 2 and 3, and R1 and R2 are different substituents through a six-step or seven-step reaction respectively. The method has the advantages of simple and convenient operation, cheap and easily-obtained raw materials and high yield of target products. Compared with the prior synthetic method, the method can synthesize methylene-bridged ferrocenyl bipyrazole that n is equal to 1 more easily, and can effectively synthesize the polymethylene-bridged ferrocenyl bipyrazole that n is more than or equal to 2, R1 and R2 are different substituents and the general formula is the Fc-[(CH2)n-R1R2PzH]2.

Description

technical field [0001] The invention relates to a polymethylene bridged ferrocenyl bispyrazole, in particular to a polymethylene bridged ferrocenyl bispyrazole and a synthesis method thereof. Background technique [0002] As shown in Figure 3, polymethylene bridged bispyrazoles with ferrocene as the skeleton (n=1, R 1 =R 2 =CH 3 ) was first synthesized by Friedrichsen et al. (Pagel, K.; Werner, A.; Friedrichsen, W.J.Organomet.Chem.1994, 481, 109; Sφrensen, H.S.; Larsen, J.; Rasmussen, B.S.; Laursen, B. ; Hansen, S.G.; Skrydstrup, T.; Amatore, C.; Jutand, A. Organometallics 2002, 21, 5243.). Ferrocene is used as raw material to go through a five-step reaction process of 1,1'-ferrocene-dicarboxylic acid, that is, ferrocene is first dicarboxylated into 1,1'-ferrocene-dicarboxylic acid, and then esterified and reduced to obtain 1 , 1'ferrocenedimethanol, then carry out alkylation reaction with acetylacetone, and finally condense with hydrazine hydrate to obtain methylene bri...

Claims

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Application Information

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IPC IPC(8): C07F17/02
Inventor 余正坤谭伟强
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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