Methoxyaniline compound and synthetic method thereof
阅读说明：本技术 一种甲氧基苯胺类化合物及其合成方法 (Methoxyaniline compound and synthetic method thereof ) 是由 黄华文 钟帅 邓国军 肖福红 陈善平 于 2021-01-06 设计创作，主要内容包括：本发明主要涉及一种甲氧基苯胺的制备方法。本发明在光催化剂及蓝光促进下,氩气氛围中,实现硝基类化合物和甲醇生成一种甲氧基苯胺的技术方案。制备得到分子结构稳定,化学性质优良的产品及其附加产品,该方法中使用光催化剂、蓝光源,为甲氧基苯胺类化合物的合成提供了一条新的路径。具有反应条件温和、反应体系简单、反应设备较少、实验操作简便等特点。本发明的甲氧基苯胺衍生物及其合成方法,可用于染料、农药、医药、橡胶助剂等多个工业生产领域；特别适合一锅法高效选择性合成甲氧基苯胺类化合物的科学研究与开发利用。(The invention mainly relates to a preparation method of methoxyaniline. The invention realizes the technical scheme that nitro compounds and methanol generate methoxyaniline in an argon atmosphere under the promotion of a photocatalyst and blue light. The prepared molecular structure is stable and chemicalThe method uses a photocatalyst and a blue light source, and provides a new path for synthesizing the methoxyaniline compound. Has the characteristics of mild reaction conditions, simple reaction system, less reaction equipment, simple and convenient experimental operation and the like. The methoxyaniline derivative and the synthesis method thereof can be used in a plurality of industrial production fields such as dye, pesticide, medicine, rubber auxiliary agent and the like; is particularly suitable for scientific research, development and utilization of synthesizing methoxyaniline compounds efficiently and selectively by a one-pot method.)
1. A methoxyaniline compound of the general formula Ia or Ib:
wherein
R is selected from hydrogen atom, halogen group, alkyl, (hetero) aryl, cyano, acetyl, alkoxy.
2. A method for synthesizing the methoxyaniline and the derivatives thereof as claimed in claim 1, which comprises the following steps under the irradiation of a photocatalyst and blue light:
(I) adding a nitro compound, methanol, a reducing agent, a catalyst, distilled water, an organic solvent and an organic acid into a reaction container;
(II) fully mixing the reactants, and carrying out blue light irradiation and heating under the protection of argon gas for reaction;
(III) purifying to obtain the product.
3. The method according to claim 2, wherein the nitro-based compound is selected from C6-C16An aromatic ring having the formula IIa or IIb:
wherein
R is selected from hydrogen atom, halogen group, alkyl, (hetero) aryl, cyano, acetyl, alkoxy.
4. The method according to claim 3, wherein the nitro compound is selected from the group consisting of: 4-bromonitrobenzene, nitrobenzene, 4-nitrobenzyl ether, 4-nitroacetophenone, 4-chloronitrobenzene, 4-nitrobenzonitrile, 2-methylnitrobenzene, 2-nitrobiphenyl.
5. The method of any one of claims 2-4, wherein the photocatalyst is: ir (ppy)3，Ir(dFCF3ppy)2(dtbbpy)PF6，4CzIPN，Rose Bengal，Ru(bpy)3·6H2O, Eosin Y.
6. A process according to any one of claims 2 to 5, wherein the organic acid is: TsOH ∙ H2O，TFA，TfOH，CH3SO3H，CH3One of COOH; the reducing agent is selected from: triphenylphosphine, tricyclohexylphosphine.
7. The process according to any one of claims 2 to 6, wherein the organic solvent is: DCM, MeCN, CHCl3One of DCE, Acetone and 1, 4-Dioxane; the dosage of the water is as follows: 0.1-0.5 mL.
8. The method according to any one of claims 2 to 7, wherein the atmosphere of the reaction vessel is: argon atmosphere; the molar ratio of the nitro compound to the photocatalyst to the organic acid to the reducing agent is 1.0:0.01-0.05:0.6-1.2:2.0-3.0, and the reaction temperature is 50-65 ℃; the reaction time is 24-36 h.
Technical Field
The invention relates to a methoxyaniline compound and a synthetic method thereof, belonging to the field of organic synthesis.
Background
The methoxyaniline and the derivative thereof are important organic compounds, and the aniline plays an important role in industrial production of dyes, perfumes, plastics, pesticides, medicines, rubber auxiliaries and the like. For example: the dye can be used for manufacturing acid ink blue G, acid medium BS, reactive brilliant red X-SB, golden light red and the like in the dye industry; in the pesticide industry for the production of many insecticides, fungicides such as DDV, aclonifen, propachlor and the like; the rubber auxiliary agents are used for preparing an antioxidant A, an antioxidant D, an accelerator M, CA and the like; can also be used as raw material of medical sulfa drug, and can be used as stabilizer in explosive and explosion-proof agent in gasoline; other compounds may also be used to produce hydroquinone, 2-phenylindole, and the like. The aniline can be used to derive N-alkylaniline, etc., which can be used as the intermediate of bactericide such as sodium diquat, insecticide such as triazophos, pyridaphenthion, herbicide such as alachlor, etc. The methods for synthesizing such compounds so far have the disadvantages of complicated synthesis steps, poor atom economy and large functional group compatibility limitations, and often require pre-functionalization of starting materials.
Disclosure of Invention
Therefore, the object of the present invention is to provide a methoxyaniline and its derivatives.
The invention also aims to provide a method for synthesizing methoxyaniline and derivatives thereof, which has the advantages of simple reaction conditions and convenient operation.
Accordingly, the invention provides a methoxyaniline and its derivatives of the general formula la or lb:
wherein
R is selected from hydrogen atom, halogen group, alkyl, (hetero) aryl, cyano, acetyl, alkoxy.
The invention also provides a method for synthesizing methoxyaniline and derivatives thereof, which comprises the following steps under the irradiation of a photocatalyst and blue light:
(I) adding a nitro compound, methanol, a reducing agent, a photocatalyst, distilled water, an organic solvent and an organic acid into a reaction container;
(II) fully mixing the reactants, and carrying out blue light irradiation and heating under the protection of argon gas for reaction;
(III) purifying to obtain the product.
Preferably, in the process of the invention, the nitro compound is selected from C6-C12An aromatic compound having the formula IIa or IIb.
Wherein
R is selected from hydrogen atom, halogen group, alkyl, (hetero) aryl, cyano, acetyl, alkoxy.
Preferably, in the method of the present invention, the nitrobenzene compound is selected from the group consisting of: 4-bromonitrobenzene, nitrobenzene, 4-nitrobenzyl ether, 4-nitroacetophenone, 4-chloronitrobenzene, 4-nitrobenzonitrile, 2-methylnitrobenzene, 2-nitrobiphenyl.
Preferably, in the process of the invention, the reducing agent is selected from: triphenylphosphine, tricyclohexylphosphine.
Preferably, in the method of the present invention, the photocatalyst is: ir (ppy)3，Ir(dFCF3ppy)2(dtbbpy)PF6，4CzIPN，Rose Bengal， Ru(bpy)3·6H2O, Eosin Y.
Preferably, in the method of the present invention, the organic acid is: TsOH. H2O，TFA，TfOH，CH3SO3H，CH3One kind of COOH.
Preferably, the present inventionThe organic solvent is: DCM, MeCN, CHCl3One of DCE, Acetone and 1, 4-Dioxane; the dosage of the water is as follows: 0.1-0.5 mL.
Preferably, in the method of the present invention, the atmosphere of the reaction vessel is: argon atmosphere; the molar ratio of the nitro compound to the photocatalyst to the organic acid to the reducing agent is 1.0:0.01-0.05:0.6-1.2: 2.0-3.0; the reaction temperature is 50-65 ℃; the reaction time is 24-36 h.
Compared with the prior art, the invention has the following beneficial effects:
(I) according to the invention, under the irradiation of a photocatalyst and blue light and in an argon atmosphere, the technical scheme of converting nitro compounds and methanol into methoxyaniline and derivatives thereof is realized, and a target product is directly and selectively synthesized in one step, so that the problem of huge waste of people, property and materials caused by the conventional multi-step synthesis method is solved, a large amount of research time is saved, and the production period is shortened; (II) under the argon atmosphere, the technical scheme that the nitro compound and the methanol compound are converted into the methoxyaniline and the derivative thereof by the photocatalyst and the blue light source has the advantages of simple reaction system, mild reaction conditions, wide material sources, remarkable increase of the added value of the product, high availability and foreseeable market commercialization prospect; the technological scheme of converting nitro compound and methanol into methoxyaniline and its derivative is scientific and reasonable, and has high radical positioning and selectivity, easy experiment operation, short reaction steps and less required apparatus. (IV) the methoxyaniline derivative and the synthesis method thereof can be used in a plurality of industrial production fields such as dye, pesticide, medicine, rubber auxiliary agent and the like; is particularly suitable for scientific research, development and utilization of synthesizing methoxyaniline compounds efficiently and selectively by a one-pot method.
Detailed Description
The present invention will now be described in further detail. The following formula is a simplified schematic, and merely illustrates the basic structure of the present invention, and therefore, it merely shows the structure related to the present invention.
Examples 1 to 16
Step 1: the nitro compound (specific substances are shown in table 1) and methanol are added into a reaction vessel, and the reducing agent (specific substances are shown in table 1), the photocatalyst (specific substances are shown in table 1), water (specific feeding amount is shown in table 1), the organic acid (specific substances are shown in table 1) and the organic solvent (specific substances are shown in table 1) are respectively added into the reaction vessel.
Step 2: the reaction vessel is heated uniformly (e.g., oil bath heated) to the temperature and under blue light as described in table 1, and the nitro compound and methanol are reacted in the solvent for the time as described in table 1; the reaction atmosphere to be explained is under argon protection.
And step 3: and (5) a purification step.
Table 1: the molar ratio of the nitro-based compound to methanol, reducing agent, photocatalyst, water, organic acid, organic solvent (nitro-compound, photocatalyst, organic acid and reducing agent), reaction temperature and reaction time in examples 1-16.
The molar ratio of the nitro compound, the photocatalyst, the organic acid and the reducing agent.
And (3) detecting the conversion rate of the substances in the reaction vessel after the step (3) and performing nuclear magnetic resonance, wherein the results of some examples are as follows:
the nuclear magnetic data of the product of example 11 are as follows:
1H NMR(400MHz,Chloroform-d)δ6.91–6.88(m,2H),6.58(d,J＝7.9Hz,1H),3.84(s,3H),3.78(br,2H)；13C NMR(100MHz,Chloroform-d)δ147.8,135.2,123.6,115.7,113.7,109.5,55.6.
the nuclear magnetic data of the product of example 12 are as follows:
1H NMR(400MHz,DMSO-d6)δ6.96(d,J＝2.5Hz,1H),6.77–6.71(m,3H),4.84(br,2H),3.64(s,4H)；13C NMR (100MHz,Chloroform-d)δ152.7,137.7,117.4,116.7,115.0,109.6,55.9.
the nuclear magnetic data of the product of example 16 are as follows:
1H NMR(400MHz,Chloroform-d)δ7.50–7.44(m,4H),7.39–7.35(m,1H),6.81–6.73(m,3H),3.79(s,3H),3.52 (br,2H)；13C NMR(100MHz,Chloroform-d)δ152.6,139.4,137.1,129.0,128.7,128.7,127.2,116.8,115.6,114.3, 55.7.
TABLE 2 conversion and products of the reactions of examples 1-16
In light of the foregoing description of the preferred embodiment of the present invention, many modifications and variations will be apparent to those skilled in the art without departing from the spirit and scope of the invention. The technical scope of the present invention is not limited to the content of the specification, and must be determined according to the scope of the claims.