Method for preparing aromatic amine compound
阅读说明：本技术 一种制备芳胺化合物的方法 (Method for preparing aromatic amine compound ) 是由 周海峰 周艳梅 皮单违 刘祈星 刘森生 于 2017-01-16 设计创作，主要内容包括：本发明提供一种制备芳胺化合物的方法,以芳硝基衍生物(I)为原料,以水为氢源和溶剂,二硼试剂为添加剂,不需要金属催化剂,反应温度在30-100℃下,反应时间4-24h即可得芳胺化合物(II),本发明中采用硼试剂中的硼原子对氧原子和氮原子有很强的亲和力,可以活化水,且硼酸是唯一的副产物,硼试剂是理想的水活化剂。与现有技术相比具有如下优点：催化剂廉价易得、反应条件温和、选择性高、成本低且产率高,适合工业化生产。(The invention provides a method for preparing aromatic amine compound, which takes aromatic nitro derivative (I) as raw material, water as hydrogen source and solvent, diboron reagent as additive, does not need metal catalyst, the reaction temperature is 30-100 ℃, the reaction time is 4-24h, and aromatic amine compound (II) can be obtained. Compared with the prior art, the method has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.)
1. The method for preparing the aromatic amine compound is characterized in that the aromatic nitro derivative (I) is used as a raw material, water is used as a hydrogen source and a solvent, a diboron reagent is used as an additive, a metal catalyst is not needed, the reaction temperature is 30-100 ℃, and the reaction time is 4-24 hours, so that the aromatic amine compound (II) can be obtained, and the specific reaction equation is as follows:
2. the process for the preparation of arylamine compounds according to claim 1 wherein [ Pd ] is]The metal catalyst is palladium acetate (Pd (OAc)2) Palladium trifluoroacetate (Pd (CF)3COO)2) Palladium/carbon (Pd/C), tris (dibenzylideneacetone) dipalladium-chloroform adduct (C)52H43Cl3O3Pd2) Bis (acetylacetonato) palladium (Pd (acac))2) Bis (triphenylphosphine) palladium dichloride (PdCl)2(PPh3)2) Tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) And any one or mixture of any several of corresponding hydrates.
3. The process for preparing arylamine compounds according to claim 1, wherein [ Cu ] is]The metal catalyst is copper trifluoromethanesulfonate (Cu (CF)3SO3)2) Copper acetate (Cu (OAc))2) Cuprous acetate (CuOAc), cupric bromide (CuBr)2) Anhydrous copper chloride (CuCl)2) Any one or a mixture of any more of copper (I) iodide (CuI), copper (I) chloride (CuCl), copper fluoride (CuF) and corresponding hydrates.
4. A process for the preparation of arylamine compounds in accordance with claim 1 wherein the boron reagent is tetrahydroxydiboron (B)2(OH)4) Boric acid (H)3BO3) Phenylboronic acid (Ph (OH)2) 4-Chlorobenzeneboronic acid (ClPh (OH))2) 2-anthraceneboronic acid, allylboronic acid pinacol ester, pinacol borane, diboron pinacol ester, bis (neopentyl glycol) diboron and any one or a mixture of any of them.
5. A process for the preparation of an arylamine compound according to claim 1, wherein Ar is selected from the group consisting of:
It is characterized in thatIn, R1Is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C1—C6Alkyl radical, C1—C6Haloalkyl, C3—C8Cycloalkyl radical, C1—C6Alkyloxy, C1—C6Alkylamino radical, formic acid C1—C6Any one of alkyl ester groups; x is O or S;
in the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine, iodine;
alkyl groups: refers to straight or branched chain alkyl;
halogenated alkyl groups: refers to straight or branched alkyl groups in which the hydrogen atoms are partially or fully substituted by halogen atoms;
cycloalkyl groups: refers to a saturated or unsaturated cycloalkyl group;
substituted aryl ketones: phenyl ketone, pyridine ketone and furan ketone.
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a method for reducing aromatic nitro into aromatic amine.
Background
Aromatic amine is also an important organic synthesis intermediate and raw material, and can be used for synthesizing various fine chemicals such as pesticides, medicines, rubber auxiliaries, dyes and pigments, synthetic resins, textile auxiliaries, surfactants, photosensitive materials and the like. In addition, aromatic amines are common building blocks in many biologically active drugs. Such as Adderall XR for treating hyperkinetic syndrome, mesalazine for resisting intestinal mucositis, and lereca for treating posttraumatic neuralgia.
Regarding the preparation of arylamine compounds, the main methods reported at present can be obtained by reducing corresponding aromatic nitro compounds, and the methods for reducing aromatic nitro compounds in industry mainly include metal (iron powder, zinc powder, etc.) reduction methods, catalytic hydrogenation reduction methods and alkali sulfide reduction methods, but there are many other reduction methods. From the viewpoint of the source of the reducing agent, hydrogen, sodium borohydride, formic acid, 9, 10-dihydroanthracene, 1, 4-dihydropyridine, thiol, (2-pyridyl) benzyl alcohol, hydrazine hydrate, trichlorosilane/triethylamine, alcohols, and the like are mainly used as the hydrogen source. However, these methods still have disadvantages: when using H2When the reducing agent is used, special high-pressure equipment and combustible gas are needed, and certain danger exists; when hydrazine hydrate is used as a reducing agent, the compound has poor selectivity if the compound contains carbon-carbon double bonds, carbon-carbon triple bonds and aldehyde groups.
Disclosure of Invention
1. The invention aims to provide a method for reducing aromatic nitro into aromatic amine, wherein the structural formula of the prepared aromatic amine compound is shown as follows:
Ar-NH2
wherein Ar is selected from the following groups:
R1is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C1—C6Alkyl radical, C1—C6Haloalkyl, C3—C8Cycloalkyl radical, C1—C6Alkyloxy, C1—C6Alkylamino radical, formic acid C1—C6Any one of alkyl ester groups; x is any one of O, S;
the invention also aims to provide the method for reducing the aromatic nitro group into the arylamine, which has the advantages of mild reaction conditions, low cost, environmental friendliness and high yield and is suitable for industrial production. The arylamine compound (II) is obtained by taking the aromatic nitro derivative (I) as a raw material, water as a hydrogen source, tetrahydroxy diboron as an additive, a palladium compound as a catalyst, and any one of toluene, ethyl acetate, acetonitrile, 2-methyltetrahydrofuran, tetrahydrofuran, chloroform, protonic solvent water, methanol or isopropanol as a solvent, and reacting for 6-24 hours at 30-70 ℃, wherein the specific reaction equation is as follows:
the Pd metal catalyst is palladium acetate (Pd (OAc)2) Palladium trifluoroacetate (Pd (CF)3COO)2) Palladium/carbon (Pd/C), tris (dibenzylideneacetone) dipalladium-chloroform adduct (C)52H43Cl3O3Pd2) Bis (acetylacetonato) palladium (Pd (acac))2) Bis (triphenylphosphine) palladium dichloride (PdCl)2(PPh3)2) Tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) And any one or mixture of any several of corresponding hydrates;
the boron reagent is tetrahydroxy diboron (B)2(OH)4) Boric acid (H)3BO3) Phenylboronic acid (Ph (OH)2) 4-Chlorobenzeneboronic acid (ClPh (OH))2) 2-anthraceneboronic acid, allylboronic acid pinacol ester, pinacol borane, diboron pinacol ester, bis (neopentyl glycol) diboron and any one or a mixture of any of them;
in the aromatic nitro derivative (I), Ar is selected from the following groups:
in the definitions of any of the compounds (I), (II) above, the terms used, whether used alone or in compound words, represent the following substituents: r1Is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C1—C6Alkyl radical, C1—C6Haloalkyl, C3—C8Cycloalkyl radical, C1—C6Alkyloxy, C1—C6Alkylamino radical, formic acid C1—C6Any one of alkyl ester groups; x is any one of O, S;
in the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine, iodine;
alkyl groups: refers to straight or branched chain alkyl;
halogenated alkyl groups: refers to straight or branched alkyl groups in which the hydrogen atoms are partially or fully substituted by halogen atoms;
cycloalkyl groups: refers to a saturated or unsaturated cycloalkyl group;
substituted aryl ketones: phenyl ketone, pyridine ketone, furan ketone;
the invention provides a new method for synthesizing arylamine compounds. Compared with the prior art, the invention has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.
The invention aims to provide a method for reducing aromatic nitro into aromatic amine, wherein the structural formula of the prepared aromatic amine compound is shown as follows:
Ar-NH2
wherein Ar is selected from the following groups:
R1is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C1—C6Alkyl radical, C1—C6Haloalkyl, C3—C8Cycloalkyl radical, C1—C6Alkyloxy, C1—C6Alkylamino radical, formic acid C1—C6Any one of alkyl ester groups; x is any one of O, S;
the invention also aims to provide the method for reducing the aromatic nitro group into the arylamine, which has the advantages of mild reaction conditions, low cost, environmental friendliness and high yield and is suitable for industrial production. Taking an aromatic nitro derivative (I) as a raw material, tetrahydroxy diboron as an additive, copper salt as a metal catalyst, acetonitrile as a solvent, and reacting at 80-100 ℃ for 24h to obtain an aromatic amine compound (II), wherein the specific reaction equation is as follows:
the Cu metal catalyst is copper trifluoromethanesulfonate (Cu (CF)3SO3)2) Copper acetate (Cu (OAc))2) Cuprous acetate (CuOAc), cupric bromide (CuBr)2) Anhydrous copper chloride (CuCl)2) Copper (I) iodide (CuI), copper (I) chloride (CuCl), copper fluoride
(CuF) and any one or a mixture of any more of the corresponding hydrates.
The boron reagent is tetrahydroxy diboron (B)2(OH)4) Boric acid (H)3BO3) Phenylboronic acid (Ph (OH)2) 4-Chlorobenzeneboronic acid (ClPh (OH))2) 2-anthraceneboronic acid, allylboronic acid pinacol ester, pinacol borane, diboron pinacol ester, bis (neopentyl glycol) diboron and any one or a mixture of any of them.
In the aromatic nitro derivative (I), Ar is selected from the following groups:
in the definitions of the compounds (I), (II) mentioned above, use is made ofThe terms, whether used alone or in compound words, represent the following substituents: r1Is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C1—C6Alkyl radical, C1—C6Haloalkyl, C3—C8Cycloalkyl radical, C1—C6Alkyloxy, C1—C6Alkylamino radical, formic acid C1—C6Any one of alkyl ester groups; x is any one of O, S.
In the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: refers to fluorine, chlorine, bromine, iodine.
Alkyl groups: refers to straight or branched chain alkyl groups.
Halogenated alkyl groups: refers to straight or branched chain alkyl groups in which the hydrogen atoms are partially or fully substituted with halogen atoms.
Cycloalkyl groups: refers to a saturated or unsaturated cycloalkyl group.
Substituted aryl ketones: phenyl ketone, pyridine ketone and furan ketone.
The invention provides a new method for synthesizing arylamine compounds. Compared with the prior art, the invention has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.
The invention aims to provide a method for reducing aromatic nitro into aromatic amine, wherein the structural formula of the prepared aromatic amine compound is shown as follows:
Ar-NH2
wherein Ar is selected from the following groups:
R1is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C1—C6Alkyl radical, C1—C6Haloalkyl, C3—C8Cycloalkyl radical, C1—C6Alkyloxy, C1—C6Alkylamino radical, formic acid C1—C6Any one of alkyl ester groups; x is any one of O, S;
the invention also aims to provide the method for reducing the aromatic nitro group into the arylamine, which has the advantages of mild reaction conditions, low cost, environmental friendliness and high yield and is suitable for industrial production. Taking the aromatic nitro derivative (I) as a raw material, taking water as a hydrogen source and a solvent, taking a diboron reagent as an additive, and obtaining the aromatic amine compound (II) at the reaction temperature of 30-100 ℃ for 4-24h without a metal catalyst, wherein the specific reaction equation is as follows:
the boron reagent is tetrahydroxy diboron (B)2(OH)4) Boric acid (H)3BO3) Phenylboronic acid (Ph (OH)2) 4-Chlorobenzeneboronic acid (ClPh (OH))2) 2-anthraceneboronic acid, allylboronic acid pinacol ester, pinacol borane, diboron pinacol ester, bis (neopentyl glycol) diboron and any one or a mixture of any of them;
in the aromatic nitro derivative (I), Ar is selected from the following groups:
in the definitions of any of the compounds (I), (II) above, the terms used, whether used alone or in compound words, represent the following substituents: r1Is hydrogen, halogen, amino, nitro, cyano, hydroxyl, mercapto, aryl ketone, substituted aryl ketone, C1—C6Alkyl radical, C1—C6Haloalkyl, C3—C8Cycloalkyl radical, C1—C6Alkyloxy, C1—C6Alkylamino radical, formic acid C1—C6Any one of alkyl ester groups; x is any one of O, S；
In the definition of the arylamine compounds, the terms used, whether used alone or in compound words, represent the following substituents:
halogen: fluorine, chlorine, bromine, iodine;
alkyl groups: refers to straight or branched chain alkyl;
halogenated alkyl groups: refers to straight or branched alkyl groups in which the hydrogen atoms are partially or fully substituted by halogen atoms;
cycloalkyl groups: refers to a saturated or unsaturated cycloalkyl group;
substituted aryl ketones: phenyl ketone, pyridine ketone, furan ketone;
the invention provides a new method for synthesizing arylamine compounds. The boron atoms in the boron reagent have strong affinity to oxygen atoms and nitrogen atoms, water can be activated, boric acid is the only byproduct, and the boron reagent is an ideal water activator. Compared with the prior art, the method has the following advantages: the catalyst is cheap and easy to obtain, the reaction condition is mild, the selectivity is high, the cost is low, the yield is high, and the method is suitable for industrial production.
Detailed Description
The following examples are intended to illustrate the invention without further limiting it.