CN111056956A - Method for preparing 2-aminobiphenyl - Google Patents
Method for preparing 2-aminobiphenyl Download PDFInfo
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- CN111056956A CN111056956A CN201811200074.4A CN201811200074A CN111056956A CN 111056956 A CN111056956 A CN 111056956A CN 201811200074 A CN201811200074 A CN 201811200074A CN 111056956 A CN111056956 A CN 111056956A
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- aminobiphenyl
- bromoaniline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of 2-aminobiphenyl, under the catalytic action of a palladium complex of nitrogen heterocyclic carbene coordination containing a carbohydrate unit, 2-bromoaniline and phenylboronic acid undergo cross coupling reaction to generate 2-aminobiphenyl, and the method is characterized in that the palladium complex of nitrogen heterocyclic carbene coordination containing α -D-pyranoaltose, β -D-pyranoaltose, α -D-pyranoidose or β -D-pyranoidose carbohydrate unit and imidazole nitrogen atoms connected to the 2-position or 3-position of a pyran ring is used as a catalyst.
Description
Technical Field
The invention relates to preparation of 2-aminobiphenyl by using palladium-catalyzed Suzuki-Miyaura cross-coupling reaction, belonging to the field of organic synthesis.
Background
2-aminobiphenyl is an important raw material for synthesizing biphenyl palladium catalysts (WO 2013184198). In 2016, Green Kaimer science and technology Inc. described the use of a catalytic amount of 0.13 mol% of CataCXium A-Pd-G2 to catalyze the reaction of 2-bromoaniline with phenylboronic acid in the presence of potassium carbonate and DMF at 50 ℃ for 8 h to obtain 2-aminobiphenyl in 98% yield (CN 105439871A). WO 2013184198 in 2013 discloses a method for obtaining 2-aminobiphenyl d by catalyzing a reaction of 2-bromoaniline and phenylboronic acid at 45 ℃ in the presence of triethylamine and tocoferol with a catalytic system consisting of 5 mol% of catalytic amount of palladium acetate and XPhos (L/Pd = 1.6). In 2009, S.W. Youn et al describe PdCl at 10 mol% in Tetrahedron Letters (2009), 50, (32), 4598-2(PPh3)2Catalyzing 2-bromoaniline and phenylboronic acid to react for 24 hours at 80 ℃ in the presence of potassium carbonate, DMF and water to obtain 2-aminobiphenyl.
The 2-aminobiphenyl is prepared by catalyzing the coupling reaction between 2-bromoaniline and phenylboronic acid by using a 1, 3-disubstituted-2H-imidazolyl-2-carbene coordinated palladium complex which has altopyranose or iduronose and one or both of imidazole nitrogen atoms are connected to the 2-position or 3-position of the pyranose as a catalyst.
Disclosure of Invention
In a first aspect, the invention provides a method for preparing 2-aminobiphenyl by using a palladium catalyst to realize cross-coupling reaction of 2-bromoaniline and phenylboronic acid under the promotion of alkali.
In a second aspect, the palladium catalyst used in the present invention is a 1, 3-disubstituted-2H-imidazolyl-2-carbene complexed palladium complex with a carbohydrate unit, characterized in that the carbohydrate unit is altopyranose or idopyranose and one or both of the nitrogen atoms of the imidazolyl group are attached at the 2-position or 3-position of the pyranose (methods of preparation are disclosed).
In a third aspect, the palladium catalyst used in the present invention is a 1, 3-disubstituted-2H-imidazolyl-2-carbene complex having an altopyranose or iduronate carbohydrate unit and having one or both of nitrogen atoms of the imidazolyl group bonded to the 2-position or 3-position of the pyranose, and the following complexes are preferable.
In a third aspect, the palladium complex with carbohydrate units used in the present invention is used in an amount of 0.003 mol% (30 ppm) to 0.02 mol% (200 ppm), preferably 0.005 mol% (50 ppm) to 0.01 mol% (100 ppm).
In a fourth aspect, the base used in the present invention according to the first aspect is potassium phosphate, potassium carbonate, sodium hydroxide or potassium hydroxide, preferably potassium phosphate and potassium carbonate.
In a fifth aspect, the solvent used in the present invention according to the first aspect is benzene, toluene, xylene, tetrahydrofuran, dioxane, ethanol, isopropanol, water or a mixture thereof, preferably a toluene mixture (by volume) with 0% to 20% water.
In a sixth aspect, according to the first aspect, the mass ratio of the 2-bromoaniline, the phenylboronic acid and the base in the invention is 1:1.0:1.2 to 1:1.5:2.0, preferably 1:1.1:1.2 to 1:1.3: 1.6.
In a seventh aspect, the reaction temperature may be in the range of 60 to 180 deg.foC is preferably in the range of 90 to 150oC。
In the eighth aspect, the reaction time may be in the range of 1 to 24 hours, preferably 3 to 12 hours.
In the ninth aspect, the reaction pressure may be from 1 to 50 atmospheres, and is generally less than 10 atmospheres.
The present invention can be illustrated in further detail by the following examples, but it is not intended that the present invention be limited to these examples.
General procedure for the Suzuki-Miyaura reaction. Phenylboronic acid (183 mg, 1.5 mmol), a base (2 mmol), 2-bromoaniline (172 mg, 1.0mmol), water (3 mmol), dodecane (85 mg, 0.5 mmol), a solvent (2 mL) and a catalyst (0.00006 mmol) were weighed into a 15mL pressure-resistant flask with a stirring magneton in this order under an air atmosphere, and the reaction was stirred at 130 ℃. The reaction mixture was cooled to room temperature, ethyl acetate (2 mL) was added thereto, the mixture was stirred for 10 minutes to terminate the reaction, and saturated brine (10 mL) was added thereto, followed by extraction with ethyl acetate (10 mL × 3). The combined organic phases are dried over anhydrous sodium sulfate and the solvent is evaporated under reduced pressure. Purifying the residue by silica gel column chromatography to obtain the product.
Claims (9)
1. The invention provides a method for preparing 2-aminobiphenyl by using a palladium catalyst to realize cross coupling reaction of 2-bromoaniline and phenylboronic acid under the promotion of alkali.
2. According to claim 1, the palladium catalyst used in the present invention is a 1, 3-disubstituted-2H-imidazolyl-2-carbene complexed palladium complex with a carbohydrate unit, characterized in that the carbohydrate unit is altopyranose or idopyranose and one or both of the nitrogen atoms of the imidazolyl group are attached at the 2-or 3-position of the pyranose.
3. According to claim 2, the palladium catalyst used in the present invention is a 1, 3-disubstituted-2H-imidazolyl-2-carbene complex having altopyranose or iduronose and having one or both of nitrogen atoms of the imidazolyl group bonded to the 2-position or 3-position of the pyranose, and includes the following complexes.
4. According to claim 2, the palladium complex with carbohydrate units used according to the invention is used in an amount of 0.003 mol% (30 ppm) to 0.02 mol% (200 ppm), preferably 0.005 mol% (50 ppm) to 0.01 mol% (100 ppm).
5. According to claim 1, the base used in the present invention is potassium phosphate, potassium carbonate, sodium hydroxide or potassium hydroxide, preferably potassium phosphate and potassium carbonate.
6. According to claim 1, the solvent used in the present invention is benzene, toluene, xylene, tetrahydrofuran, dioxane, ethanol, isopropanol, water or a mixture thereof, preferably a toluene solvent with 0% to 20% water (by volume).
7. According to claim 1, the mass ratio of 2-bromoaniline, phenylboronic acid and base in the present invention is 1:1.0:1.2 to 1:1.5:2.0, preferably 1:1.1:1.2 to 1:1.3: 1.6.
8. The reaction temperature in the invention can be 60-180 DEGoC is preferably in the range of 90 to 150oC。
9. The reaction time in the present invention may be in the range of 1 to 24 hours, preferably 3 to 12 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811200074.4A CN111056956A (en) | 2018-10-16 | 2018-10-16 | Method for preparing 2-aminobiphenyl |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811200074.4A CN111056956A (en) | 2018-10-16 | 2018-10-16 | Method for preparing 2-aminobiphenyl |
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| CN111056956A true CN111056956A (en) | 2020-04-24 |
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| CN201811200074.4A Pending CN111056956A (en) | 2018-10-16 | 2018-10-16 | Method for preparing 2-aminobiphenyl |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939786A (en) * | 2021-02-03 | 2021-06-11 | 江苏先导药业有限公司 | Preparation method of 2-aminobiphenyl derivative and 2-hydroxybiphenyl derivative |
-
2018
- 2018-10-16 CN CN201811200074.4A patent/CN111056956A/en active Pending
Non-Patent Citations (3)
| Title |
|---|
| AU NAVEEN, KANAGARAJ等: ""Synthesis of 4-Alkylidene-Substituted 1,2,3,4-Tetrahydroisoquinolines via", 《SYNTHESIS》 * |
| ZUO, ZHIJUN等: ""Highly Stereoselective Synthesis of Imine-Containing Dibenzo[b,d]azepines", 《ANGEWANDTE CHEMIE, INTERNATIONAL EDITION》 * |
| 张德智等: ""环金属、N-杂环卡宾配位的 Pd(II)络合物的合成、结构与催化性能"", 《中国化学会•第八届有机化学学术会议暨首届重庆有机化学国际研讨会》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939786A (en) * | 2021-02-03 | 2021-06-11 | 江苏先导药业有限公司 | Preparation method of 2-aminobiphenyl derivative and 2-hydroxybiphenyl derivative |
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