A kind of method that adopts oxidative halogenation method to prepare haloaryl compound

A technology of halogenated aryl and compound, which is applied in the field of fine chemical synthesis to achieve the effects of good selectivity, mild reaction conditions and high yield

Inactive Publication Date: 2011-11-30
EAST CHINA NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In addition, the solvents currently used for halogen

Method used

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  • A kind of method that adopts oxidative halogenation method to prepare haloaryl compound
  • A kind of method that adopts oxidative halogenation method to prepare haloaryl compound
  • A kind of method that adopts oxidative halogenation method to prepare haloaryl compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1～6

[0012] Add 2 mmol catalyst, 5 mmol anisole, 10 mmol sodium bromide, 10 mmol hydrogen peroxide (30% aqueous solution) and 3 mL water into the round bottom flask, react for 3 hours at room temperature and constant speed, and then stand still , Extract twice with 15mL ether, combine the ether extracts, analyze with gas chromatography to determine the yield of bromoanisole; after gas chromatography analysis, the ether phase is saturated with NaHCO 3 The solution and water are washed separately, dried with anhydrous sodium sulfate, distilled to remove the ether, and then distilled under reduced pressure to obtain pure p-bromoanisole. The lower water phase (containing catalyst) can continue to be recycled. Table 1 shows the results of the aqueous oxidative bromination reaction of anisole and sodium bromide using different bifunctional imidazolium ionic liquids as catalysts.

[0013] Table 1 Aqueous oxidation bromination results of anisole and sodium bromide with different bifunctional...

Embodiment 7～15

[0020] Table 2 gives the catalyst 6 Under the action of, the oxidative halogenation reaction of different halogenated salts or halogen acids and anisole in the water phase results. Add 2 mmol catalyst 6 , 5 mmol anisole, 10 mmol halogenated salt (or halogen acid), 10 mmol hydrogen peroxide (30% aqueous solution) and 3 mL water were added to the round bottom flask, and the oxidation was carried out according to the steps and conditions of Examples 1 to 6. Halogenation reaction.

[0021] Table 2 catalyst 6 Aqueous oxidation and halogenation reaction results of different halogenated salts or halogen acids and anisole under action a

[0022]

[0023] a 2 mmol catalyst 6 , 5 mmol anisole, 10 mmol halogenated salt (or hydrohalic acid), 10 mmol hydrogen peroxide (30%), 3 mL water, room temperature, reaction time 3 hours.

[0024] b Gas chromatography analysis.

[0025]

Embodiment 16～30

[0027] Table 3 gives the catalyst 6 The oxidative bromination reaction results of hydrobromic acid and anisole in different ionic liquids under the action of. Add 0.5 mmol catalyst 6 , 5 mmol anisole, 5 mmol hydrobromic acid, 7.5 mmol hydrogen peroxide (30% aqueous solution) and 3 mL different ionic liquids were added to the round-bottom flask, and the oxidative bromination reaction was carried out according to the steps and conditions of Examples 1 to 6. .

[0028] table 3 catalyst 6 Oxidative bromination results of hydrobromic acid and anisole in different ionic liquids under action a

[0029]

[0030] a 0.5 mmol catalyst 6 , 5 mmol anisole, 5 mmol hydrobromic acid, 7.5 mmol hydrogen peroxide (30%), 3 mL ionic liquid, room temperature, reaction time 3 hours.

[0031] b Bmim=1-methyl-3-butylimidazole quaternary ammonium cation; Bpy=N-butylpyridine quaternary ammonium cation.

[0032] c OAc=Acetate, OTs=Toluenesulfonate, NTf 2 = Trifluoromethanesulfonimide anion.

[0033] d Gas c...

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PUM

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Abstract

The invention discloses a method for preparing halogenated aryl compounds through oxidation and halogenation. In the method, chlorine gas, bromine water or elementary iodine are prevented from serving as a halogenating agent, and in an aqueous phase or ionic liquid reaction medium, bidirectional ionic liquid is taken as a catalyst, hydrogen peroxide (commercial 30 percent aqueous solution) is taken as an oxidant, aryl compounds and halogeno salt (or haloid acid) are subjected to oxidation and halogenation to form the halogenated aryl compounds. The method is a green synthesis method; and the prepared halogenated aryl has high selectivity and yield, reaction conditions are mild, volatile organic solvents are not needed in the reaction, and the catalyst can be recycled.

Description

technical field [0001] The invention belongs to the technical field of fine chemical synthesis, and specifically relates to a new green synthesis method for preparing halogenated aryl compounds by using hydrogen peroxide as an oxidant to realize the catalyzed oxidation halogenation reaction of aryl compounds and halogenated salts. Background technique [0002] Halogenated aryl compounds are an important class of organic intermediates, which have very important uses in the synthesis of fine chemicals, medicine, pesticides and other industries, and are also necessary raw materials for various coupling reactions. With chlorine gas, bromine water or iodine element (Cl 2 、Br 2 or I 2 ) The electrophilic substitution reaction of aryl compounds for halogenating reagents is the most direct and commonly used method for synthesizing halogenating reagent compounds, but chlorine gas, bromine water or iodine as halogenating reagents are highly toxic, difficult to operate and use, and d...

Claims

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Application Information

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IPC IPC(8): C07B39/00C07C41/22C07C43/225C07C25/02C07C17/00C07C25/06C07C25/22C07C39/27C07C37/62C07C45/63C07C49/807C07C205/11C07C201/12
CPCY02P20/584
Inventor 刘晔王玲王洒洒路勇
Owner EAST CHINA NORMAL UNIV
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