Synthetic method of ferrocene derivatives

A technology for ferrocene derivatives and synthesis methods, which is applied in the field of synthesis of ferrocene derivatives, and can solve the problems of inability to synthesize, poor universality of synthesis methods, low purity of monochloroferrocene, etc.

Active Publication Date: 2014-02-26
DAAN GENE CO LTD
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

The third is that Tao's invention does not involve the synthetic method of bromoferrocene derivatives and iodoferrocene derivatives, and the synthetic method has poor applicability
They are different from Tao in that they did not remove ferrocene by washing and filtering, so the final ferrocene monochloride contains a large amount of ferrocene, and ferrocene and ferrocene monochloride cannot be separated , the purity of the synthesized ferrocene monochloride is very low, and the synthesis of D2, D3, D4, etc. cannot be carried out at all; in addition, they only did the synthesis of D1

Method used

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  • Synthetic method of ferrocene derivatives
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  • Synthetic method of ferrocene derivatives

Examples

Experimental program
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Effect test

Embodiment 1

[0039] Example 1: Synthesis of DA1

[0040] Synthesis of D21: Under anhydrous and anaerobic conditions, put 20g (107.5mmol) of ferrocene into a 2L round-bottom reaction flask and dissolve it with 200mL of anhydrous DCM, and add 15.4mL (161.3mmol) dropwise while stirring at 0°C. ) of 3-chloropropionyl chloride, drop it in 15 minutes, then add 21.5g (161mmol) anhydrous aluminum trichloride in batches, react for 2 hours, then add dropwise 215mL (215mmol, the concentration of borane in tetrahydrofuran is 1.0mol / L) borane tetrahydrofuran, the dropwise addition time is 1.5 hours, and after the dropwise reaction is completed for another 2 hours, it is quenched with ice water, washed, filtered, extracted, dried, and spin-dried. Dissolve the spin-dried substance with 200mL of N,N-dimethylformamide and 50mL of acetone, add 32.2g (214.7mmol) of NaI and react at 95°C for 3 hours, cool down to room temperature and oxidize with 60mL of 4mol / L hydrogen The sodium solution was hydrolyzed fo...

Embodiment 2

[0052] Embodiment 2: the synthesis of DA2

[0053] Synthesis of D12: Under anhydrous and oxygen-free conditions, put 60g (322.6mmol) ferrocene into the reaction flask and dissolve it with 300mL anhydrous tetrahydrofuran, add 372.2mL (1.3mol / L, 483.9mmol ) tert-butyllithium for 1 hour, warming up to room temperature for 2 hours, then cooling to -78°C, adding 122.9g (483.9mmol) biboronic acid pinacol ester for 1 hour, then naturally warming up to room temperature for 2 hours. The reaction was quenched with ice water, and then the quenched solution was washed, filtered, extracted, dried, and spin-dried, and silica gel was used as the filling phase, and the ferrocene was first rinsed with n-hexane to remove ferrocene, and then 25% DCM / Rinse with n-hexane, spin dry, and recrystallize to obtain pure ferrocene biboronic acid pinacol ester. 40g (128.2mmol) of the obtained pure ferrocene biboronic acid pinacol ester was dissolved in a 2000mL three-necked round-bottomed flask with 50m...

Embodiment 3

[0071] Embodiment 3: the synthesis of DA3

[0072] Synthesis of D13: Under anhydrous and anaerobic conditions, put 50g (268.8mmol) of ferrocene into a reaction flask and dissolve it in 250mL of anhydrous tetrahydrofuran, and add 252mL (n-butyllithium concentration of 1.6mol) at -5°C / L, 403.2mmol) n-butyllithium was reacted for 1 hour, heated to room temperature and reacted for 2 hours, then cooled to -78°C, added 101.6g (400mmol) pinacolate borate, reacted for 1 hour, and naturally heated to room temperature for reaction 2 Hour. The reaction was quenched with ice water, and then the quenched solution was washed, filtered, extracted, dried, and spin-dried, and silica gel was used as the filling phase. Rinse with methane / n-hexane, and finally rinse with 10% ethyl acetate / n-hexane, spin dry, and recrystallize until pure ferrocene disubstituted diboronic acid pinacol ester. The obtained pure ferrocene disubstituted diboronic acid pinacol ester 60g (137mmol) was dissolved in 200...

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Abstract

The invention relates to a synthetic method of ferrocene derivatives. Ferrocene is used as a raw material for the ferrocene derivatives. The ferrocene derivatives which can be used for labeling special nucleotides are prepared by steps of: treating the ferrocene with a lithium reagent and bis(pinacolato)diboron to obtain a halogenated ferrocene; performing Friedel-Crafts acylation, Clemmensen reduction and hydrolysis under an alkaline condition to obtain a halogenated ferrocene alkyl alcohol; reacting with nitrophenyl chloroformate and N-hydroxy succinimide to obtain ferrocene succinimide carbonate; condensing with an alcohol amine reagent to obtain a ferrocene alkylolamide carbonate; performing substitution, oxidation, and other reactions by reacting with a phosphoramidite reagent to obtain a phosphorous ferrocene reagent; reacting with 5-chloromercuri-2'-deoxyuridine to obtain a deoxyuridine phosphorous ferrocene reagent; modifying the 5' end of the deoxyuridine through DMT-C1 to obtain a DMT-modified deoxyuridine phosphorous ferrocene reagent; and finally performing substitution by reacting with the phosphoramidite reagent. The method has operation safety, convenience, high product purity and high yield. The method has a wider application scope than other synthetic methods.

Description

technical field [0001] The invention relates to a method for synthesizing ferrocene derivatives, which belongs to the technical field of organic chemistry and also belongs to the technical field of biochemistry. Background technique [0002] Ferrocene derivatives have broad application prospects in biology, medicine, microbiology and other fields. Mainly based on the unique structure and properties of ferrocene derivatives: the aromaticity makes it easier to undergo substitution reactions; the sandwich structure makes it have a certain thickness, which can prevent ferrocene derivatives from approaching the active sites of certain enzymes, and has a strong selective Sex; lipophilicity enables it to pass through the cell membrane smoothly, and act with various enzymes, DNA, RNA and other substances in the cell, so it may be used as a drug for treating certain diseases. In addition, ferrocene derivatives have unique electrochemical and photochemical properties. Based on this ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F17/02
Inventor 陈华云李明程琛肖湘文陈俊
Owner DAAN GENE CO LTD
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