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Synthesis method of diaryl aniline compound

A technology of diarylaniline and synthesis method, which is applied to the synthesis of diarylaniline compounds and the synthesis field of amine compounds, can solve the problems of limited substrate expansion, narrow substrate range, low utilization efficiency and the like, and achieves good industrialization Prospect, effect of high product yield and short reaction time

Active Publication Date: 2013-10-09
JIAXING NIYA OPTOELECTRONICS CO LTD
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AI Technical Summary

Problems solved by technology

[0006] In 2001, Collman et al. realized [Cu(OH)·TMEDA] under aqueous conditions 2 Cl 2 C-N coupling reaction of aryl boronic acid and imidazole under catalysis, the reaction conditions are mild, no need to add additional alkali, the disadvantage is that the yield of the product is medium, and the utilization efficiency is not high
[0010] In 2003, Biffis et al. used Cu(OAc) 2 The exchanged functional resin MPI–Cu(1:1) catalyzes the C-N coupling reaction of arylboronic acid and arylamine. The method can be completed at room temperature, air and without alkali participation, but the disadvantage is that the yield of the reaction is not high. Not ideal, narrow substrate range
[0040] As mentioned above, a variety of methods for the synthesis of arylanilines have been disclosed in the prior art, but there are still some defects in these methods, for example, only amino compounds can be used as substrates, which greatly limits the expansion of substrates; or the reaction steps Too much and too many materials in the system, etc., which limit the yield of the final target product

Method used

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  • Synthesis method of diaryl aniline compound
  • Synthesis method of diaryl aniline compound
  • Synthesis method of diaryl aniline compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0077] Embodiment 1: the synthesis of diphenylamine

[0078]

[0079] In a dry and clean flask, add 50ml of solvent 1,4-dioxane, and then add the above formula (II) compound, formula (III) compound, Cu(acac) 2 and potassium tert-butoxide so that the molar ratio is 1:2:0.05:2, wherein the compound of formula (II) is 10mmol, nitrogen replacement is performed three times, and then the reaction system is stirred at 80°C under the protection of continuous feeding of nitrogen React for 14 hours.

[0080] After the reaction is finished, filter, and the filtrate is used to remove the solvent by a rotary evaporator, and the residue is purified by 200-300 mesh silica gel column chromatography to obtain the target product as a solid, with a yield of 98.2% and a purity of 98.9% (HPLC) .

[0081] Melting point: 52-53°C;

[0082] NMR: 1 H NMR (CDCl 3 ,500MHz):δ7.23-7.26(m,4H),7.04-7.09(m,4H),6.93(m,2H),5.69(s,1H);

[0083] 13 C NMR (CDCl 3 , 125MHz) δ143.2(2C), 129.4(4C), 121.0(4...

Embodiment 2

[0084] Example 2: Synthesis of phenyl m-tolyl-amine

[0085]

[0086] In a dry and clean flask, add 50ml of solvent 1,4-dioxane, and then add the above formula (II) compound, formula (III) compound, Cu(acac) 2 and potassium tert-butoxide, so that the molar ratio is 1:3:0.1:3, wherein the compound of formula (II) is 10mmol, nitrogen replacement is three times, and then under the protection of continuously feeding nitrogen, the reaction system is stirred at 90°C React for 13 hours.

[0087] After the reaction, filter, and use a rotary evaporator to remove the solvent from the filtrate, and purify the residue through 300-400 mesh silica gel column chromatography to obtain the target product with a yield of 95.3% and a purity of 98.2% (HPLC).

[0088] NMR: 1 H NMR (CDCl 3 ,500MHz):δ7.27-7.24(m,2H),7.15(t,J=7.9Hz,1H),7.06(d,J=7.7Hz,2H),6.93-6.88(m,3H),6.75( d,J=7.5Hz,1H),5.73(s,1H),2.31(s,3H);

[0089] 13 C NMR (CDCl 3 , 125MHz) δ143.2, 143.1, 139.2, 129.3 (2C), 129.1, 12...

Embodiment 3

[0090] Example 3: Synthesis of phenyl-p-methoxyphenyl-amine

[0091]

[0092] In a dry and clean flask, add 50ml of solvent 1,4-dioxane, and then add the above formula (II) compound, formula (III) compound, Cu(acac) 2 and potassium tert-butoxide, so that the molar ratio is 1:4:0.15:4, wherein the compound of formula (II) is 10mmol, and the nitrogen is replaced three times, and then the reaction system is stirred at 100°C under the protection of continuously feeding nitrogen React for 12 hours.

[0093] After the reaction was completed, filter, and use a rotary evaporator to remove the solvent from the filtrate, and purify the residue through 400-500 mesh silica gel column chromatography to obtain the target product with a yield of 96.4% and a purity of 99.1% (HPLC).

[0094] NMR: 1 H NMR (CDCl 3 ,500MHz):δ7.21-7.27(m,2H),7.07-7.11(m,2H),6.95-6.84(m,5H),5.52(s,1H),3.83(s,3H);

[0095] 13 C NMR (CDCl 3, 125MHz) δ144.0, 140.3, 130.9, 129.9 (2C), 129.3 (2C), 120.3 (2C), 1...

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Abstract

The invention relates to a synthesis method of a diaryl aniline compound. The method comprises steps of with copper acetylacetonate (Cu(acac)2) as a catalyst, enabling a nitrobenzene compound to react with a phenylboronic acid compound in an organic solvent in the presence of alkali, thus preparing the diaryl aniline compound. The method has the advantages of high product yield, high purity, simple reaction, simpleness and convenience for operation, short reaction duration and the like, thus providing a brand-new synthesis method for preparation of like compounds; and the synthesis method has a good industrialization prospect and a potential application value.

Description

technical field [0001] The invention relates to a method for synthesizing amine compounds, in particular to a method for synthesizing diarylaniline compounds, and belongs to the field of organic chemical synthesis. Background technique [0002] Aromatic amines are a very important class of organic and pharmaceutical intermediates, which are widely used in the synthesis of medicines, pesticides, dyes and the synthesis of ligands used in transition metal-catalyzed reactions. For its synthetic method, the Buchwald-Hartwig cross-coupling reaction is an important method for the synthesis of aromatic amines, but the complex ligands or halogenated hydrocarbons used as substrates in this method are relatively polluting to the environment, which greatly limits promotion of this method. [0003] On the basis of the above defects, people have developed a process route using aryl boronic acid, because aryl boronic acid has many advantages such as low toxicity, mild use conditions, stab...

Claims

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Application Information

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IPC IPC(8): C07C211/55C07C209/00C07C217/82C07C213/02C07C223/06C07C221/00
Inventor 陈久喜吴华悦王兴永刘妙昌高文霞黄小波
Owner JIAXING NIYA OPTOELECTRONICS CO LTD
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