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Preparation method of aromatic halogenated compound

A technology of aromatic halogenated compounds, which is applied in the field of preparation of aromatic halogenated compounds, can solve problems such as difficult operation and severe reaction conditions, and achieve the effects of high reaction efficiency, low reaction cost, and convenient and simple operation

Active Publication Date: 2011-03-30
PEKING UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the currently known synthetic methods, most of them are to use aromatic hydrocarbons to react with halogen sources (chlorine, liquid bromine or N-halogenated succinimide, etc.) under the catalysis of Lewis acid to obtain aromatic halogenated compounds. The disadvantage is that a large amount of Lewis acid catalysts are used, sometimes even more equivalent catalysts are needed for relatively inert substrates, and the reaction conditions are relatively severe (chlorine gas, liquid bromine, strong Lewis acid environment), and it is not easy to operate

Method used

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  • Preparation method of aromatic halogenated compound
  • Preparation method of aromatic halogenated compound
  • Preparation method of aromatic halogenated compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0032] Synthesis of p-Bromoanisole

[0033] Add 534mg (i.e. 3mmol) N-bromosuccinimide in the long tube type reaction bottle of 25mL, add 6mL1,2-dichloroethane solvent, then take by weighing 324mg (i.e. 3mmol) anisole, finally Add 0.1 mg of gold trichloride (dissolve 1 mg of gold trichloride in 1 mL of 1,2-dichloroethane, take out 0.1 mL with a micro syringe and inject into the system), heat the reaction at 80°C, and wait for the completion of the reaction as monitored by GC-MS (about 20 hours). Concentrate after the reaction, and use petroleum ether as an eluent for column chromatography purification to obtain p-bromoanisole, whose structure is shown in the following formula:

[0034]

[0035] The compound is a colorless liquid with a yield of 96%, and its NMR data are as follows:

[0036] 1 H NMR (300MHz, CDCl 3 )δ7.37(d, 2H, J=8.8Hz), 6.78(d, 2H, J=8.8Hz), 3.78(s, 3H); 13 C NMR (50MHz, CDCl 3 )δ158.6, 132.1, 115.6, 112.7, 55.3;

Embodiment 2

[0038] Synthesis of methyl 2-methoxy-5-bromobenzoate

[0039] Add 534mg (3mmol) N-bromosuccinimide, 1mg (0.003mmol) of gold trichloride to a 25mL long tube reaction flask, add 6mL 1,2-dichloroethane solvent, and finally weigh 498 mg (3 mmol) of methyl 2-methoxybenzoate was reacted at 80° C., and the reaction was completed by GC-MS monitoring (about 23 hours). Concentrate after the reaction, and use sherwood oil: ethyl acetate volume ratio as the eluent column chromatography purification of 20: 1, can obtain 2-methoxy-5-bromobenzoic acid methyl ester, its structure is shown in the following formula:

[0040]

[0041] The compound is a colorless liquid with a yield of 96%, and its NMR data are as follows:

[0042] 1 H NMR (200MHz, CDCl 3 )δ7.90(d, 1H, J=2.6Hz), 7.55(dd, 1H, J 1 =2.6Hz,J 2 =8.9Hz), 6.87(d, 1H, J=8.9Hz), 3.89(s, 6H); 13 C NMR (50MHz, CDCl 3 )δ165.1, 158.1, 135.9, 134.1, 121.6, 113.8, 112.1, 56.1, 52.1.

Embodiment 3

[0044] Synthesis of 4-bromo-1,2-methylenedioxybenzene

[0045] Add 356mg (2mmol) N-bromosuccinimide, 3mg (0.01mmol) of gold trichloride to a 25mL long-tube reaction flask, add 4mL of 1,2-dichloroethane solvent, and finally weigh 244 mg (2 mmol) of 1,2-methylenedioxybenzene was reacted at room temperature, and the reaction was completed by GC-MS monitoring (about 4 hours). Concentrate after the reaction, and purify by column chromatography using petroleum ether as the eluent to obtain 4-bromo-1,2-methylenedioxybenzene, whose structure is shown in the following formula:

[0046]

[0047] The compound is a colorless liquid with a yield of 92%, and its NMR data are as follows:

[0048] 1 H NMR (200MHz, CDCl 3 )δ6.98~6.92(m, 2H), 6.69(d, 1H, J=8.7Hz), 5.97(s, 2H); 13 CNMR (50MHz, CDCl 3 )δ146.9, 124.3, 113.0, 112.2, 110.3, 109.5, 101.5.

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Abstract

The invention discloses a preparation method of an aromatic halogenated compound. Arene Ar-H and N-halogenated succimide are reacted in an organic solvent under the catalysis of auric chloride to obtain an aromatic halogenated compound Ar-X, wherein Ar represents substituted or unsubstituted non-heterocycle aryl and X represents chlorine, bromine or iodine. The reaction in the method does not need strict water-free and oxygen-free condition and occurs successfully in air. The invention has the advantages of good tolerance and universality to functional groups, little use amount of the catalyst and lower reaction cost, is simple and convenient for operation, and can be widely used for preparing the aromatic halogenated compound.

Description

technical field [0001] The invention belongs to the field of organic synthesis, in particular to a preparation method of an aromatic halogenated compound. Background technique [0002] Aromatic halogenated compounds are a very important class of chemical raw materials, which are widely used in scientific research and industrial production. In scientific research, aromatic halogenated compounds are mainly used in organic synthesis. They can be used as molecular building blocks to participate in a wide variety of organic chemical reactions to construct more complex target compounds; in industrial production, aromatic halogenated compounds are mainly used in dyes , materials, medicine and pesticide industries. For a long time, people have continuously improved and perfected the synthesis methods of aromatic halogenated compounds. In the currently known synthetic methods, most of them are to use aromatic hydrocarbons to react with halogen sources (chlorine, liquid bromine or N...

Claims

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Application Information

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IPC IPC(8): C07B39/00C07C43/225C07C41/22C07C69/92C07C67/307C07D317/62C07F5/04C07C25/22C07C17/12B01J27/10
Inventor 莫凡洋邱頔严明韬张艳王剑波
Owner PEKING UNIV
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