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Method for synthesizing 2-((9-hydrofluorene-9-yl) methyl) malonate

A synthesis method and technology of malonate are applied in the preparation of carboxylic acid esters, chemical instruments and methods, and the preparation of organic compounds. It can solve the problems of poor economy and large amounts of reaction waste, and achieve mild reaction conditions and suitable Mass production and high atom economy

Active Publication Date: 2019-09-20
WENZHOU UNIVERSITY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0011] However, the use of Wittig reagent will generate a large amount of reaction waste, and the use of expensive transition metals also makes the method less economical

Method used

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  • Method for synthesizing 2-((9-hydrofluorene-9-yl) methyl) malonate
  • Method for synthesizing 2-((9-hydrofluorene-9-yl) methyl) malonate
  • Method for synthesizing 2-((9-hydrofluorene-9-yl) methyl) malonate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0042]

[0043] Add stirring magnet and above formula (I) compound (0.3mmol) in Schlenk tube, nitrogen protection, add dichloromethane (3mL), then add trifluoromethanesulfonic acid (1.8mmol, 6 molar equivalents) under stirring, then Seal, and stir at room temperature for 1 hour. The solvent and trifluoromethanesulfonic acid were distilled off under reduced pressure, and the residue was purified by column chromatography to obtain the compound of formula (II) with a yield of 95%.

[0044] 1 H NMR (400MHz, CDCl 3)δ7.76(d, J=7.4Hz, 2H), 7.54(d, J=7.4Hz, 2H), 7.38(t, J=7.4Hz, 2H), 7.31(t, J=7.4Hz, 2H) ,4.09(m,3H),3.99-3.94(m,2H),3.19(t,J=7.3Hz,1H),2.68-2.65(m,2H),1.15(t,J=7.1Hz,6H). 13 C NMR (125MHz, CDCl 3 )δ 169.36, 145.51, 141.29, 127.40, 126.95, 124.86, 119.91, 61.35, 48.86, 45.34, 31.69, 13.89.

Embodiment 2

[0046]

[0047] Add a stirring magnet, dichloromethane (80mL) and trifluoromethanesulfonic acid (60mmol, 6 molar equivalents) into a Schlenk tube under nitrogen protection, and then dissolve the compound of formula (I) (10mmol) in dichloromethane (10mL) , added to the reaction tube under stirring, then sealed, and stirred at room temperature for 1 hour. The reaction system was quenched with saturated sodium bicarbonate solution under ice-water bath cooling, the product was extracted with ethyl acetate (60 mL×2), the organic phases were combined, washed with saturated sodium chloride solution (60 mL×2), and dried over anhydrous sodium sulfate. The solvent was distilled off under reduced pressure to obtain the compound of formula (II) with a yield of 98%.

[0048] 1 H NMR (400MHz, CDCl 3 )δ7.76(d, J=7.4Hz, 2H), 7.54(d, J=7.4Hz, 2H), 7.38(t, J=7.4Hz, 2H), 7.31(t, J=7.4Hz, 2H) ,4.09(m,3H),3.99-3.94(m,2H),3.19(t,J=7.3Hz,1H),2.68-2.65(m,2H),1.15(t,J=7.1Hz,6H). 13 C NMR (125MH...

Embodiment 3

[0050]

[0051] Add a stirring magnet and the above formula (I) compound (0.3mmol) to the Schlenk tube, nitrogen protection, add dichloromethane (3mL), then add trifluoromethanesulfonic acid (3mmol, 10 molar equivalents) under stirring, and then seal , Stir the reaction at room temperature for 1 hour. The solvent and trifluoromethanesulfonic acid were distilled off under reduced pressure, and the residue was purified by column chromatography to obtain the compound of formula (II) with a yield of 90%.

[0052] 1 H NMR (400MHz, CDCl 3 )δ7.76(d, J=7.5Hz, 2H), 7.52(d, J=7.4Hz, 2H), 7.38(t, J=7.3Hz, 2H), 7.31(t, J=7.4Hz, 2H) ,4.04(t,J=5.7Hz,1H),3.52(s,6H),3.15(t,J=7.2Hz,1H),2.72(dd,J=5.9Hz,J=7.0Hz,2H). 13 C NMR (125MHz, CDCl 3 ) δ 169.72, 145.21, 141.32, 127.44, 126.95, 124.79, 119.95, 52.36, 48.25, 45.31, 31.57.

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Abstract

The invention discloses a method for synthesizing 2-((9-hydrofluorene-9-yl) methyl) malonate. By adopting the method, synthesis of the 2-((9-hydrofluorene-9-yl) methyl) malonate is achieved through an open-loop cyclization reaction of 2-biaryl cyclopropyl-1,1-dicarboxylic ester under a strong base reaction condition. The method specifically comprises the following steps: by taking dichloromethane as a reaction solvent, adding trifluoromethanesulfonic acid of a 1-10 mole equivalent weight, and carrying out a reaction under a room temperature condition, so as to obtain a target product. The method is easy in raw material obtaining, simple to operate, high in yield and wide in universality. Particularly in preparation of a gram grade or greater, the method is very reliable, and in addition, separation and purification means are simple.

Description

technical field [0001] The invention belongs to the technical field of organic chemical synthesis, and specifically refers to a synthesis method of 2-((9-hydrofluoren-9-yl)methyl)malonate. Background technique [0002] Compounds containing 3-(9-hydrofluoren-9-yl)propionyl structure have important application value in medicinal chemistry. Smith et al. synthesized a compound with a 3-(9-hydrofluoren-9-yl) propionate structure, which has a strong inhibitory effect on mammalian ribonucleotide reductase, IC 50 = 40-50 μM (Bioorg. Med. Chem. Lett. 2005, 15, 5146-5149). Vederas et al. synthesized a polypeptide containing a 3-(9-hydrofluoren-9-yl) propionamide structure, which has a good inhibitory effect on Escherichia coli and Campylobacter jejuni (J.Med.Chem.2014,57,1127- 1131). [0003] The current synthesis methods of 3-(9-hydrofluorene-9-yl)propionic acid or its esters all need to start with 9-hydrofluorene or its analogues as raw materials. Matsumoto et al. use 9-hydroflu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C67/333C07C69/616C07C69/734C07C69/732C07C69/65C07C201/12C07C205/56C07D333/78C07D209/70
CPCC07C67/333C07C201/12C07D209/70C07D333/78C07C2603/18C07C2603/52C07C69/616C07C69/734C07C69/732C07C69/65C07C205/56
Inventor 李欢
Owner WENZHOU UNIVERSITY