CN113860980B - Method for preparing arylamine compound by photoinduction reduction C-N coupling reaction - Google Patents
Method for preparing arylamine compound by photoinduction reduction C-N coupling reaction Download PDFInfo
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- CN113860980B CN113860980B CN202111181471.3A CN202111181471A CN113860980B CN 113860980 B CN113860980 B CN 113860980B CN 202111181471 A CN202111181471 A CN 202111181471A CN 113860980 B CN113860980 B CN 113860980B
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- C07B43/00—Formation or introduction of functional groups containing nitrogen
- C07B43/04—Formation or introduction of functional groups containing nitrogen of amino groups
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- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/325—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups reduction by other means than indicated in C07C209/34 or C07C209/36
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- C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes
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- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D213/74—Amino or imino radicals substituted by hydrocarbon or substituted hydrocarbon radicals
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Abstract
The invention discloses a method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction, which comprises the following steps: firstly, weighing nitro compounds, boric acid compounds and reducing agents with the mass ratio of 1:1-3:5-9, placing the nitro compounds, the boric acid compounds and the reducing agents into a reactor with a vacuum valve, adding an organic solvent which is 8-10 times of the total mass of the organic solvent, and uniformly mixing reaction substrates through stirring; then connecting the reactor filled with the mixed liquid to a gas exchange device through a pressure-resistant double-joint pipe, and exchanging air in the reactor by using inert gas to obtain reaction mother liquor; and then placing the reactor with the reaction mother liquor under a light source with the wavelength of 200-500 nm, and continuously stirring for 6-24 h to obtain the arylamine compound. The photocatalysis reaction is a one-pot synthesis method, has simple operation and high yield, and effectively avoids the problem of heat loss caused by using high-temperature reaction.
Description
Technical Field
The invention belongs to the field of photocatalytic organic synthesis, and particularly relates to a method for preparing an arylamine compound by a photoinduced reduction C-N coupling reaction.
Background
Arylamine compounds are important synthesis intermediates in the industries of chemical industry, agrochemical industry, pharmacy, fine chemicals, photoelectric materials and the like. In recent years, the global requirement for diphenylamine rises year by year, the market scale reaches 15 hundred million yuan by 2020, and the estimated 2026 can reach 21 hundred million yuan, the annual composite growth rate (CAGR) is 4.9%, and the market requirement for diphenylamine has a straight-line rising trend. Therefore, the synthesis of such nitrogen-containing compounds has received a great deal of attention and is continually pushing the innovation of the synthesis methods. The most common methods for preparing aromatic amine compounds include Buchwald-Hartwig reaction, chan-Lam reaction, ullmann reaction route, reductive amination reaction using nitroaromatic hydrocarbon as raw material, etc. which require a certain high temperature to assistAnd the catalyst drives the reaction. For example, a small ring organophosphorus based catalyst (1,2,2,3,4,4-hexamethylphosphine alkane) and a terminal hydrosilane reducing agent (phenylsilane) reported by Radosevich et al (j.am. Chem. Soc.2018,140, 15200-15205) drive intermolecular coupling of nitroarenes with boric acid. Organic MoO reported by Sanz et al (Angew. Chem.2019,131, 2151-2155) 2 Cl 2 (dmf) 2 The bpy homogeneous phase catalyzes the direct amination of boric acid with nitro compounds. Patent CN109232275B discloses a preparation method of 4-nitrodiphenylamine and 4-nitrosodiphenylamine, which comprises the following steps: (1) Dissolving anhydride and aniline in an organic solvent, and carrying out ammonolysis reaction for 30-240 min at 100-200 ℃; (2) Adding nitrobenzene and a catalyst into the solution obtained in the step (1), adding strong alkali, and performing condensation reaction for 0.5-10 h at 30-150 ℃ to generate 4-nitrodiphenylamine and 4-nitrosodiphenylamine; (3) Mixing the mixed solution obtained in the step (2) with a sodium hydroxide solution, carrying out hydrolysis reaction at 20-80 ℃ under stirring, separating a water phase and an oil phase, and distilling the oil phase under reduced pressure to remove the organic solvent and unreacted aniline, thereby obtaining a mixture of 4-nitrodiphenylamine and 4-nitrosodiphenylamine. The invention has complex synthesis process, higher cost and difficult catalyst separation, and does not meet the requirements of modern green chemical industry.
Disclosure of Invention
The invention aims at solving the technical problems and provides a method for preparing an arylamine compound by an efficient photoinduced reduction C-N coupling reaction.
The invention reduces the problems of high energy consumption caused by complex synthesis method, unstable catalyst structure caused by using catalyst, low catalyst recycling and reutilization, metal residue and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction comprises the following steps:
step 1, weighing nitro compounds, boric acid compounds and reducing agents with the mass ratio of 1:1-3:5-9, placing the nitro compounds, the boric acid compounds and the reducing agents in a reactor with a vacuum valve, adding an organic solvent which is 8-10 times of the total mass of the organic solvent, and uniformly mixing reaction substrates through stirring;
step 2: connecting a reactor filled with mixed liquid to a gas exchange device through a pressure-resistant double-joint pipe, and exchanging air in the reactor by using inert gas to obtain reaction mother liquor;
step 3: the reactor with the reaction mother liquor is placed under a light source with the wavelength of 200-500 nm, the light source surrounds the reactor in a surrounding manner, the illumination distance is 5-50cm, and mechanical stirring is used for continuously stirring for 6-24 h, so that the arylamine compound is obtained.
Further, in the step 1, the nitro compound is any one of 4-fluoronitrobenzene, 3-bromonitrobenzene, 4-chloronitrobenzene, 4-methylnitrobenzene, 4-methoxynitrobenzene, 4-nitrobenzenesulfonic acid methyl ester, 4-nitrobenzoic acid methyl ester, 4-ethylnitrobenzene, 2-chloro-5 nitropyridine and 4-nitrobenzotrifluoride; the boric acid compound is any one of phenylboronic acid, triphenylborate, 4-methoxyphenylboronic acid, 4-fluorobenzeneboronic acid, 3-bromophenylboronic acid and 2-methylpyridine-3-boric acid; the reducing agent is one or more of triphenylphosphine, hydrazine hydrate, sodium borohydride and phenylsilane in any proportion; the organic solvent is one or more of dimethyl sulfoxide, toluene, cyclopentyl methyl ether, tetrahydrofuran, acetonitrile and N-N dimethylformamide in any proportion.
Further, the light source for photocatalysis in the step 3 is selected from any one of a xenon lamp, an LED lamp, a mercury lamp and a halogen tungsten lamp;
further, the calculation of the yield of the arylamine compound obtained in the step 3 can be obtained by an internal standard-NMR quantitative or column chromatography method, wherein the internal standard is selected from any one of 4-fluorotoluene, 1,3, 5-trimethoxybenzene and tetraethoxysilane, and the addition amount of the internal standard is 0.3-1.5 times of that of the nitro compound.
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
(1) The invention uses nitrobenzene compound containing a series of substituents as reaction raw materials, thereby avoiding the problems of toxicity caused by directly using aniline and energy consumption caused by easy oxidation.
(2) The photocatalysis reaction of the invention is a one-pot synthesis method, and has simple operation and wide universality.
(3) The invention does not use any catalyst, photosensitizer and the like, and can drive the reaction to proceed by using illumination with a certain wavelength range and has considerable yield.
Detailed Description
The following is a detailed description of a method for preparing arylamine compounds by photoinduced reduction C-N coupling reaction according to the present invention by means of specific examples:
example 1
A method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction comprises the following specific steps:
at room temperature, 3 parts of 4-fluoronitrobenzene, 37mg of phenylboric acid and 157mg of triphenylphosphine are respectively weighed and placed in three 10ml reaction tubes with vacuum valves, the three reaction tubes are marked as reaction 1, reaction 2 and reaction 3 in sequence, toluene is added into the reaction 1 tube, cyclopentyl methyl ether is added into the reaction 2 tube, tetrahydrofuran is added into the reaction 3 tube according to 8 times of the total mass, and then ultrasonic mixing is carried out uniformly. The reaction tube was then connected to a double row of tubes filled with nitrogen, the air in the reaction tube was evacuated and filled with 1bar nitrogen by a continuous operation of vacuum-aeration with nitrogen. Then placing the reaction tube (reaction 1, reaction 2 and reaction 3) under an LED lamp with 365nm, and continuously stirring for 24 hours at an illumination distance of 5-50cm to obtain the arylamine compound.
The beneficial effects of this embodiment are:
after the reaction is finished, 22mg of 4-fluorotoluene is respectively added into the reaction liquids of the reaction 1, the reaction 2 and the reaction 3 to serve as internal standards, and then the internal standards and the reaction liquids are uniformly mixed by ultrasonic again for 5-10 min. Sampling F 19 The NMR was quantitatively calculated from the characteristic peaks of the standard nuclear magnetism of the product, and yields of the target products (reaction 1, reaction 2 and reaction 3) were 90%, 99% and 85%, respectively.
Example 2
A method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction comprises the following specific steps:
27mg of 4-methylnitrobenzene, 32mg of 2-chloro-5-nitropyridine and 38mg of 4-nitrobenzotrifluoride are weighed at room temperature and placed in three 10ml reaction tubes with vacuum valves respectively, the reaction tubes are marked as reaction 4, reaction 5 and reaction 6 in sequence, 37mg of phenylboric acid, 157mg of triphenylphosphine and toluene solution with the total mass being 8 times of that are added, and then the mixture is uniformly mixed by ultrasound. The reaction tube was then connected to a double row of tubes filled with nitrogen, the air in the reaction tube was evacuated and filled with 1bar nitrogen by a continuous operation of vacuum-aeration with nitrogen. Then placing the reaction tube (reaction 1, reaction 2 and reaction 3) under an LED lamp with 365nm, and continuously stirring for 24 hours at an illumination distance of 5-50cm to obtain the arylamine compound.
The beneficial effects of this embodiment are:
after the reaction is finished, the yield of the reaction 5 is 72% by adopting a column chromatography; reaction 4 and reaction 6 are calculated by NMR-internal standard method, namely, 37mg of 1,3, 5-trimethoxybenzene is added into reaction 4, 22mg of 4-fluorotoluene is added into reaction 6 as internal standard, and then the internal standard and the reaction solution are uniformly mixed by ultrasonic again for 5-10 min. Sampling H 1 NMR (reaction 4), F 19 The NMR (reaction 6) was quantitatively calculated from the characteristic peaks of the standard nuclear magnetism of the product, and the yields of the target products (reaction 4, reaction 6) were 80% and 96%, respectively.
Example 3
A method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction comprises the following specific steps:
at room temperature, three parts of 28mg of 4-fluoronitrobenzene, 46mg of 4-methoxyphenylboric acid and 157mg of triphenylphosphine are respectively weighed and placed in three 10ml reaction tubes with vacuum valves, the three reaction tubes are marked as reaction 7, reaction 8 and reaction 9 in sequence, toluene solution is added into the three reaction tubes according to 8 times of the total mass, and then ultrasonic mixing is carried out uniformly. The reaction tube was then connected to a double row of tubes filled with nitrogen, and the air in the reaction tube was evacuated and filled with nitrogen by a continuous operation of vacuum-introducing nitrogen. Then placing reaction 7 under 254nm LED lamp, reaction 8 under 365nm LED lamp, and illumination distance of 5-50cm, and placing reaction 9 under 450nm LED lamp, and continuously stirring for 24h to obtain arylamine compound.
The beneficial effects of this embodiment are:
after the reaction is finished, 22mg of 4-fluorotoluene is added to the reaction 7, the reaction 8 and the reaction 9 as an internal standard, and then the internal standard and the reaction liquid are uniformly mixed by ultrasonic again for 5-10 min. Sampling F 19 The NMR was quantitatively calculated from the characteristic peaks of the standard nuclear magnetism of the product, and yields of the target products (reaction 7, reaction 8 and reaction 9) were 20%, 90% and 45%, respectively.
Example 4
A method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction comprises the following specific steps:
157mg of triphenylphosphine, hydrazine hydrate and phenylsilane are weighed at room temperature, placed in three 10ml reaction tubes with vacuum valves, marked as reaction 1, reaction 10 and reaction 11 in sequence, then 28mg of 4-fluoronitrobenzene, 37mg of phenylboric acid and toluene solution with the total mass being 8 times of that of the materials are added, and then mixed uniformly by ultrasound. The reaction tube was then connected to a double row of tubes filled with nitrogen, and the air in the reaction tube was evacuated and filled with nitrogen by a continuous operation of vacuum-introducing nitrogen. Then placing the reaction (reaction 1, reaction 10 and reaction 11) under an LED lamp with 365nm, and continuously stirring for 24 hours at an illumination distance of 5-50cm to obtain the arylamine compound.
The beneficial effects of this embodiment are:
after the reaction is finished, 22mg of 4-fluorotoluene is added to the reaction 1, the reaction 10 and the reaction 11 as an internal standard, and then the internal standard and the reaction liquid are uniformly mixed by ultrasonic again for 5-10 min. Sampling F 19 The NMR was quantitatively calculated from the characteristic peaks of the standard nuclear magnetism of the product, and yields of the target products (reaction 1, reaction 10 and reaction 11) were divided into 90%, 36% and 68%.
Example 5
A method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction comprises the following specific steps:
at room temperature, 3 parts of 4-fluoronitrobenzene, 37mg of phenylboric acid and 157mg of triphenylphosphine are respectively weighed and placed in 3 reaction tubes with vacuum valves, wherein the reaction tubes are respectively marked as reaction 12, reaction 1 and reaction 13, toluene is added into the three reaction tubes according to 8 times of the total mass, and then ultrasonic mixing is carried out uniformly. The reaction tube was then connected to a double row of tubes filled with nitrogen, and the air in the reaction tube was evacuated and filled with nitrogen by a continuous operation of vacuum-introducing nitrogen. Then placing the reaction tubes (reaction 12, reaction 1 and reaction 13) under an LED lamp of 365nm, wherein the illumination distance is 5-50cm, continuously stirring the reaction tubes for 6 hours, continuously stirring the reaction tube for 12 hours, continuously stirring the reaction tube for 1 hour, continuously stirring the reaction tube for 24 hours, and respectively obtaining the arylamine compounds.
The beneficial effects of this embodiment are:
after the reaction is finished, 22mg of 4-fluorotoluene is respectively added into the reaction 12, the reaction 1 and the reaction 13 as internal standard, and then the internal standard and the reaction liquid are uniformly mixed by ultrasonic again for 5-10 min. Sampling F 19 The NMR was quantitatively calculated from the characteristic peaks of the standard nuclear magnetism of the product, and the yields of the target products (reaction 12, reaction 1 and reaction 13) were 31%, 54% and 72%.
The invention provides a thought and a method for preparing an arylamine compound by photoinduction reduction C-N coupling reaction, and particularly the method and the way for realizing the technical scheme are numerous, the above is only a preferred embodiment of the invention, and it should be pointed out that a plurality of improvements and modifications can be made by those skilled in the art without departing from the principle of the invention, and the improvements and the modifications are also considered as the protection scope of the invention. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (4)
1. A method for preparing arylamine compounds by photoinduction reduction C-N coupling reaction is characterized by comprising the following steps:
step 1, weighing nitro compounds, boric acid compounds and reducing agents with the mass ratio of 1:1-3:5-9, placing the nitro compounds, the boric acid compounds and the reducing agents in a reactor with a vacuum valve, adding an organic solvent which is 8-10 times of the total mass of the organic solvent, and uniformly mixing reaction substrates through stirring;
step 2, connecting the reactor filled with the mixed liquid to a gas exchange device through a pressure-resistant double-joint pipe, and exchanging air in the reactor by using inert gas to obtain reaction mother liquor;
step 3, placing the reactor with the reaction mother liquor under a light source with the light wavelength of 200-500 nm, wherein the light source surrounds the reactor in a surrounding manner, the illumination distance is 5-50cm, and mechanical stirring is used for continuously stirring for 6-24 hours to obtain an arylamine compound;
the nitro compound is any one of 4-fluoronitrobenzene, 3-bromonitrobenzene, 4-chloronitrobenzene, 4-methylnitrobenzene, 4-methoxynitrobenzene, 4-nitrobenzenesulfonic acid methyl ester, 4-nitrobenzoic acid methyl ester, 4-ethylnitrobenzene, 2-chloro-5 nitropyridine and 4-nitrobenzotrifluoride;
the boric acid compound is any one of phenylboronic acid, triphenylborate, 4-methoxyphenylboronic acid, 4-fluorobenzeneboronic acid, 3-bromophenylboronic acid and 2-methylpyridine-3-boric acid;
the reducing agent is one or more of triphenylphosphine, hydrazine hydrate, sodium borohydride and phenylsilane in any proportion;
the organic solvent is one or more of dimethyl sulfoxide, toluene, cyclopentyl methyl ether, tetrahydrofuran, acetonitrile and N-N dimethylformamide in any proportion.
2. The method for preparing an arylamine compound by photoinduction reduction C-N coupling reaction according to claim 1, which is characterized in that: in the step 2, the inert gas is nitrogen, helium, neon or argon.
3. The method for preparing an arylamine compound by photoinduction reduction C-N coupling reaction according to claim 1, which is characterized in that: in the step 3, the rotating speed of the mechanical stirring is 600-1500 r/min.
4. The method for preparing an arylamine compound by a photoinduction reduction C-N coupling reaction according to claim 1, wherein in the step 3, the light source is any one of a xenon lamp, an LED lamp, a mercury lamp and a halogen tungsten lamp.
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| JP2010155985A (en) * | 2008-12-04 | 2010-07-15 | Mitsubishi Chemicals Corp | Arylamine polymer, organic light emitting device material, composition for organic light emitting device, organic light emitting device, organic el display, and organic electroluminescence illumination |
| CN106800493A (en) * | 2017-01-16 | 2017-06-06 | 三峡大学 | A kind of method that fragrant nitro is reduced to arylamine |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010155985A (en) * | 2008-12-04 | 2010-07-15 | Mitsubishi Chemicals Corp | Arylamine polymer, organic light emitting device material, composition for organic light emitting device, organic light emitting device, organic el display, and organic electroluminescence illumination |
| CN106800493A (en) * | 2017-01-16 | 2017-06-06 | 三峡大学 | A kind of method that fragrant nitro is reduced to arylamine |
Non-Patent Citations (2)
| Title |
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| Copper anchored on phosphorus g-C3N4 as a highly efficient photocatalyst for the synthesis of N-arylpyridin-2-amines;Jia-Qi Di等;Green Chemistry;第23卷(第2期);1041-1049 * |
| Intermolecular Reductive C-N Cross Coupling of Nitroarenes and Boronic Acids by PIII/PV=O Catalysis;Nykaza, Trevor V.等;Journal of the American Chemical Society;第140卷(第45期);15200-15205 * |
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