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Halogenated aromatic ring compound and preparation method thereof

A technology of halogenated aromatic rings and compounds, which is applied in the preparation of carbon-based compounds, organic compounds, halogenated hydrocarbons, etc., to achieve the effects of simplifying the synthesis reaction route, simplifying the synthesis steps, and improving drug compatibility

Inactive Publication Date: 2014-08-06
TSINGHUA UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The activity of chlorination reagents is much lower than that of iodination reagents, so the chlorination modification of aromatic rings is rarely reported in the literature

Method used

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  • Halogenated aromatic ring compound and preparation method thereof
  • Halogenated aromatic ring compound and preparation method thereof
  • Halogenated aromatic ring compound and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Embodiment 1, preparation formula 1 compound

[0033]

[0034] Formula 1

[0035] 90mg of ethyl benzoate, 40mg of N-chlorosuccinimide, 3.4mg of Pd(OAc) 2 Add 160mg of selective fluorine reagent to a sealed tube, add 1,2-dichloroethane to dissolve; add 53uL trifluoromethanesulfonic acid under stirring, seal it, and stir at 90°C for 3h. In this reaction system, ethyl benzoate, N-chlorosuccinimide, Pd(OAc) 2 , The molar ratio of trifluoromethanesulfonic acid and selective fluorine reagent is 2:1:0.05:2.0:1.5. After the reaction was completed, 1,2-dichloroethane was added to quench the reaction, and the remaining acid and salt were washed away with saturated aqueous sodium bicarbonate solution, and extracted twice with 1,2-dichloromethane. The extracts were combined, dried with anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The residue was separated and purified by silica gel chromatography (n-hexane:ether (volume ratio 200:1)) to obtain ...

Embodiment 2

[0039] Embodiment 2, preparation formula 2 compound

[0040]

[0041] Formula 2

[0042] 60mg of ethyl benzoate, 36mg of N-bromosuccinimide, 2.3mg of Pd(OAc) 2 Add 106mg of selective fluorine reagent to a sealed tube, add 1,2-dichloroethane, dissolve; add 35uL trifluoromethanesulfonic acid while stirring, seal, and stir at 90°C for 4h. In this reaction system, ethyl benzoate, N-chlorosuccinimide, Pd(OAc) 2 , The molar ratio of trifluoromethanesulfonic acid and selective fluorine reagent is 2:1:0.05:2.0:1.5. After the reaction was completed, 1,2-dichloroethane was added to quench the reaction, and the remaining acid and salt were washed away with saturated aqueous sodium bicarbonate solution, and extracted twice with 1,2-dichloromethane. The extracts were combined, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The residue was separated and purified by silica gel chromatography (n-hexane:ether (volume ratio 200:1)) to obtain 35 mg of...

Embodiment 3

[0046] Embodiment 3, preparation formula 3 compound

[0047]

[0048] Formula 3

[0049] 88mg of ethyl p-toluate, 40mg of N-chlorosuccinimide, 3.4mg of Pd(OAc) 2 Add 108mg of sodium persulfate to a sealed tube, add 1,2-dichloroethane to dissolve; add 40uL trifluoromethanesulfonic acid while stirring, seal it, and stir at 70°C for 4h. In this reaction system, ethyl p-toluate, N-chlorosuccinimide, Pd(OAc) 2 , The molar ratio of trifluoromethanesulfonic acid and sodium persulfate is 2:1:0.05:1.5:1.5. After the reaction was completed, 1,2-dichloroethane was added to quench the reaction, and the remaining acid and salt were washed away with saturated aqueous sodium bicarbonate solution, and extracted twice with 1,2-dichloromethane. The extracts were combined, dried with anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. The residue was separated and purified by silica gel chromatography (n-hexane:ether (volume ratio 200:1)) to obtain 40 mg of the com...

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PUM

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Abstract

The invention discloses a halogenated aromatic ring compound shown as formula I and a preparation method thereof. In the formula I, DG represents COOR, CONHR, CH2COOR, SO2NHR, -CO-, -CHO(-CH=N-R) or a group shown as formula III; R1 is H, C1-C5 saturated alkane, F, Cl, Br or I; both R2 and R4 are H, C1-C5 saturated alkane, OR, F Cl, Br, or I; R3 is H, F, Cl, Br, I, CF3, NO2 or C1-C5 saturated alkane; wherein R is H or C1-C5 alkane; and X is Cl or Br. The preparation method of the halogenated aromatic ring compound shown as formula I includes the step of: making a compound shown as formula II react with a halogenation reagent in the presence of a palladium catalyst, a cocatalyst and an oxidizing agent to obtain the halogenated aromatic ring compound shown as formula I. The halogenated aromatic ring compound provided by the invention can be used for preparation of a series of halogen atom-containing compounds with a biphenyl structure, thus having important significance in study of estrogen receptors and discovery of drugs.

Description

technical field [0001] The invention relates to a preparation method of halogenated aromatic ring compounds. Background technique [0002] The construction of C-C bonds and C-X bonds by activating C-H bonds with transition metals such as palladium, rhodium, and ruthenium has become a hot direction in the development of organic methodology in recent years. In this method, the metal (M) forms a cyclic intermediate with the positioning group (DG) and the C-H bond that needs to be activated. The positioning group fixes M in the cyclic intermediate. If the positioning group has a higher ability to fix M Stronger, the easier it is to activate the corresponding C-H bond. The coordination ability of N atom and metal is stronger than that of other atoms. Therefore, the positioning group containing N atom was developed first, such as pyridine ring and pyrimidine ring. However, this also limits the flexibility of the positioning group, because these N-containing positioning groups ar...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C69/76C07C69/65C07C67/307C07C231/12C07C233/65C07C237/42C07C233/54C07C233/76C07C235/84C07C311/16C07C303/40C07C49/807C07C45/63C07B39/00
CPCC07C17/263C07C25/18C07C49/807C07C49/813C07C69/65C07C69/76C07C233/54C07C233/65C07C233/76C07C235/84C07C237/42C07C311/16
Inventor 饶燏孙秀云
Owner TSINGHUA UNIV
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