CN117820127A - Preparation method of aromatic amine compound - Google Patents
Preparation method of aromatic amine compound Download PDFInfo
- Publication number
- CN117820127A CN117820127A CN202311721198.8A CN202311721198A CN117820127A CN 117820127 A CN117820127 A CN 117820127A CN 202311721198 A CN202311721198 A CN 202311721198A CN 117820127 A CN117820127 A CN 117820127A
- Authority
- CN
- China
- Prior art keywords
- reaction
- aromatic amine
- amine compound
- aromatic
- triethylsilane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- -1 aromatic amine compound Chemical class 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 29
- 239000011630 iodine Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000005580 one pot reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims description 37
- 238000005070 sampling Methods 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 30
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 20
- 238000010586 diagram Methods 0.000 claims description 19
- 238000004440 column chromatography Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 51
- 238000010438 heat treatment Methods 0.000 description 17
- 238000004090 dissolution Methods 0.000 description 16
- 238000000926 separation method Methods 0.000 description 12
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- BUIRECPWKPHZGT-UHFFFAOYSA-N (2-nitrosophenyl)-phenyldiazene Chemical compound N(=O)C1=C(C=CC=C1)N=NC1=CC=CC=C1 BUIRECPWKPHZGT-UHFFFAOYSA-N 0.000 description 1
- NTBYINQTYWZXLH-UHFFFAOYSA-N 1,2-dichloro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C(Cl)=C1 NTBYINQTYWZXLH-UHFFFAOYSA-N 0.000 description 1
- RZKKOBGFCAHLCZ-UHFFFAOYSA-N 1,4-dichloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(Cl)=CC=C1Cl RZKKOBGFCAHLCZ-UHFFFAOYSA-N 0.000 description 1
- NTKADLOYTKVXQN-UHFFFAOYSA-N 1-bromo-2-methoxy-4-nitrobenzene Chemical compound COC1=CC([N+]([O-])=O)=CC=C1Br NTKADLOYTKVXQN-UHFFFAOYSA-N 0.000 description 1
- SWXVEPMSQBEVRH-UHFFFAOYSA-N 1-bromo-3-fluoro-5-nitrobenzene Chemical compound [O-][N+](=O)C1=CC(F)=CC(Br)=C1 SWXVEPMSQBEVRH-UHFFFAOYSA-N 0.000 description 1
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 description 1
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 1
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 1
- AVYGCQXNNJPXSS-UHFFFAOYSA-N 2,5-dichloroaniline Chemical compound NC1=CC(Cl)=CC=C1Cl AVYGCQXNNJPXSS-UHFFFAOYSA-N 0.000 description 1
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- AKCRQHGQIJBRMN-UHFFFAOYSA-N 2-chloroaniline Chemical compound NC1=CC=CC=C1Cl AKCRQHGQIJBRMN-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- SDYWXFYBZPNOFX-UHFFFAOYSA-N 3,4-dichloroaniline Chemical compound NC1=CC=C(Cl)C(Cl)=C1 SDYWXFYBZPNOFX-UHFFFAOYSA-N 0.000 description 1
- NGZAVSDIXFIWHJ-UHFFFAOYSA-N 3-bromo-5-fluoroaniline Chemical compound NC1=CC(F)=CC(Br)=C1 NGZAVSDIXFIWHJ-UHFFFAOYSA-N 0.000 description 1
- RQKFYFNZSHWXAW-UHFFFAOYSA-N 3-chloro-p-toluidine Chemical compound CC1=CC=C(N)C=C1Cl RQKFYFNZSHWXAW-UHFFFAOYSA-N 0.000 description 1
- FSGTULQLEVAYRS-UHFFFAOYSA-N 4,5-dichloro-2-nitroaniline Chemical compound NC1=CC(Cl)=C(Cl)C=C1[N+]([O-])=O FSGTULQLEVAYRS-UHFFFAOYSA-N 0.000 description 1
- IWFHBRFJOHTIPU-UHFFFAOYSA-N 4,5-dichlorobenzene-1,2-diamine Chemical compound NC1=CC(Cl)=C(Cl)C=C1N IWFHBRFJOHTIPU-UHFFFAOYSA-N 0.000 description 1
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 description 1
- BFQSQUAVMNHOEF-UHFFFAOYSA-N 4-bromo-2,6-difluoroaniline Chemical compound NC1=C(F)C=C(Br)C=C1F BFQSQUAVMNHOEF-UHFFFAOYSA-N 0.000 description 1
- UXLRNUCHBXKRBL-UHFFFAOYSA-N 4-bromo-2-fluoro-6-nitroaniline Chemical compound NC1=C(F)C=C(Br)C=C1[N+]([O-])=O UXLRNUCHBXKRBL-UHFFFAOYSA-N 0.000 description 1
- WDFQBORIUYODSI-UHFFFAOYSA-N 4-bromoaniline Chemical compound NC1=CC=C(Br)C=C1 WDFQBORIUYODSI-UHFFFAOYSA-N 0.000 description 1
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 description 1
- LLIOADBCFIXIEU-UHFFFAOYSA-N 4-fluoro-3-nitroaniline Chemical compound NC1=CC=C(F)C([N+]([O-])=O)=C1 LLIOADBCFIXIEU-UHFFFAOYSA-N 0.000 description 1
- KRZCOLNOCZKSDF-UHFFFAOYSA-N 4-fluoroaniline Chemical compound NC1=CC=C(F)C=C1 KRZCOLNOCZKSDF-UHFFFAOYSA-N 0.000 description 1
- ABAGKHWCTWMUDH-UHFFFAOYSA-N 5-bromo-1,3-difluoro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=C(F)C=C(Br)C=C1F ABAGKHWCTWMUDH-UHFFFAOYSA-N 0.000 description 1
- OZKZRRLKJAXHQA-UHFFFAOYSA-N 5-bromo-3-fluorobenzene-1,2-diamine Chemical compound NC1=CC(Br)=CC(F)=C1N OZKZRRLKJAXHQA-UHFFFAOYSA-N 0.000 description 1
- PEDMFCHWOVJDNW-UHFFFAOYSA-N 5-fluoro-2-nitroaniline Chemical compound NC1=CC(F)=CC=C1[N+]([O-])=O PEDMFCHWOVJDNW-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 description 1
- BNUHAJGCKIQFGE-UHFFFAOYSA-N Nitroanisol Chemical compound COC1=CC=C([N+]([O-])=O)C=C1 BNUHAJGCKIQFGE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- RNVCVTLRINQCPJ-UHFFFAOYSA-N o-toluidine Chemical compound CC1=CC=CC=C1N RNVCVTLRINQCPJ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The preparation method of aromatic amine compound uses aromatic hydrocarbon nitro compound as raw material, and under the condition of room temperature in triethylsilane and iodine simple substance system, the aromatic amine compound can be obtained by means of one-step reaction; on the premise of obtaining good yield, the method has the advantages of simple and convenient operation of the whole steps, mild reaction process and easy preparation.
Description
Technical Field
The invention belongs to the field of organic compound preparation, and particularly relates to a preparation method of aromatic amine compounds.
Background
Aromatic amines are important intermediates in the fine chemical, dye and pigment industries. Amine substances widely exist in nature and have wide biological activity. Reduction of nitrobenzene to aniline is one of the most important reactions in aromatic chemistry. The nitro reduction method is numerous, and specifically comprises: the metal is added with hydrochloric acid for reduction, and the common metal is zinc, iron and the like, so that the metal is suitable for compounds stable to acid; with catalytic hydrogenation, such as Pt, ni, etc., catalysts, mild reduction may reduce only nitro groups. There are also some characteristic reduction reactions of nitrobenzene, such as reduction with zinc to phenylhydroxylamine under weakly acidic conditions; reducing under alkaline condition, obtaining azobenzene from aqueous solution, obtaining hydroazobenzene from alcohol solution.
However, in the nitroreduction method, various reaction transition states such as nitroso, azobenzene, and ammonia are unavoidable, a plurality of reaction points can be usually seen when the reaction is tracked, the reaction time is prolonged properly, and the intermediates are generally reduced thoroughly, but metal ions are difficult to recover, and some technologies have great limitations in safety and operation.
Triethylsilane is an inexpensive, stable, low-toxicity substance that is commonly used as a scavenger. On the other hand, due to its association withThe compatibility of acids, transition metals (e.g., pd, pt, mo, ni, au, mn, rh, ru, os and Ir) and their complexes, triethylsilane, which is also widely used as a reducing agent for chemical reactions, is beneficial in various fields, such as modern natural product synthesis, pharmaceutical chemistry, and the like, as well as the ability to protect (silylate) and derivatize various compounds (e.g., alcohols, phenols, thiols, amines, carbonyls, carboxylic acids, amides, olefins, and enols). Triethylsilane has been used as a substitute reductant for the hydrogenation of olefins and C-N/C-O/S-O groups and for the regioselective hydrogenation of multifunctional scaffolds in the past forty years, with great development prospects.
Maryam Mirza-Aghayana et al (Palladium-catalyzed reduction of nitroaromatic compounds to the corresponding anilines) reported the use of PdCl in 2010 2 -Et 3 The SiH system reduces nitroaromatics to the corresponding amines under mild conditions. Different nitroaromatics at 10mol% PdCl 2 Et in the presence of ethanol 3 SiH reacts directly at room temperature with high yields, but requires the use of an inert atmosphere and anhydrous solvents, and is limited to nitroaromatics.
CN 1660771a reported in 2004 that nitrobenzene undergoes a high temperature reduction reaction in the presence of an alcohol solution and a catalyst, wherein the catalyst is: pt/Al 2 O 3 NiB, renay-Ni. Although the invention reduces the reaction steps and simplifies the production process, the reaction temperature is higher, which is easy to cause resource waste and is unfavorable for green production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a preparation method of aromatic amine compounds.
The invention adopts the following technical scheme:
the preparation process of aromatic amine compound includes one-step reaction of aromatic nitro compound as material in triethylsilane and iodine simple system at room temperature to obtain aromatic amine compound.
Further, the reduction reaction process is specifically as follows: at room temperature, adding aromatic nitro compound and solvent into a reactor, stirring, and adding triethylsilane and iodine simple substance into a reaction system after dissolving; after the addition, stirring is continued, and sampling GC tracking is carried out; and after the reaction is stopped, separating by column chromatography to obtain the aromatic amine compound.
Further, in the reduction reaction, the ratio of the amounts of triethylsilane and aromatic nitro compound used was 8.0:1.0.
further, in the reduction reaction, the ratio of the amounts of the iodine simple substance and the aromatic nitro compound used was 0.5:1.0.
further, in the reduction reaction, the solvent is dichloroethane.
Further, during the reduction reaction, the mass ratio of the volume of the solvent to the aromatic nitro compound is 8.0-15.0mL:1.0g.
As can be seen from the above description of the present invention, compared with the prior art, the present invention has the following beneficial effects: according to the invention, aromatic hydrocarbon nitro compounds are used as raw materials, and aromatic amine compounds are obtained through one-step reaction under the conditions of a triethylsilane and iodine simple substance system and room temperature. On the premise of obtaining good yield, the whole steps are simple and convenient to operate, the reaction process is mild, and the preparation is easy.
Drawings
FIG. 1 is a synthetic route diagram of the present invention;
FIG. 2 is a synthetic route diagram of example 1;
FIG. 3 is a synthetic route diagram of example 2;
FIG. 4 is a synthetic route diagram of example 3;
FIG. 5 is a synthetic route diagram of example 4;
FIG. 6 is a synthetic route diagram of example 5;
FIG. 7 is a synthetic route diagram of example 6;
FIG. 8 is a synthetic route diagram of example 7;
FIG. 9 is a synthetic route diagram of example 8;
FIG. 10 is a synthetic route diagram of example 9;
FIG. 11 is a synthetic route diagram of example 10;
FIG. 12 is a synthetic route diagram of example 11;
FIG. 13 is a synthetic route diagram of example 12;
FIG. 14 is a synthetic route diagram of example 13;
FIG. 15 is a synthetic route diagram of example 14;
FIG. 16 is a synthetic route diagram of example 15;
FIG. 17 is a synthetic route diagram of example 16;
FIG. 18 is a synthetic route diagram of example 17.
Detailed Description
The invention is further described below by means of specific embodiments.
The preparation method of aromatic amine compound uses aromatic hydrocarbon nitro compound as raw material, and under the condition of triethylsilane and iodine simple substance system and room temperature, the aromatic amine compound can be obtained by means of one-step reaction; with specific reference to FIG. 1, the synthetic route pattern in FIG. 1 may be H, F, cl, br, NH for X, Y, Z 2 、NO 2 Or OMe.
The reduction reaction process is specifically as follows: at room temperature, adding aromatic nitro compound and solvent into a reactor, stirring, and adding triethylsilane and iodine simple substance into a reaction system after dissolving; after the addition, stirring is continued, and sampling GC tracking is carried out; and after the reaction is stopped, separating by column chromatography to obtain the aromatic amine compound.
Specifically, the ratio of the amounts of triethylsilane and aromatic nitro compound used in the reduction reaction was 8.0:1.0; the ratio of the amounts of the substances of the elementary iodine and of the aromatic nitro compound used was 0.5:1.0; the solvent is dichloroethane; the mass ratio of the volume of the solvent to the aromatic hydrocarbon nitro compound is 8.0-15.0mL:1.0g.
Example 1
The synthetic roadmap is specifically referred to in fig. 2.
The reduction reaction process is specifically as follows: 246mg of nitrobenzene and 4mL of dichloroethane are added into a reactor at room temperature, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into the reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction was stopped, aniline was obtained by column chromatography separation, and the reaction yield was 66%.
Example 2
The synthetic roadmap is specifically referred to in fig. 3.
The reduction reaction process is specifically as follows: 282mg of p-fluoronitrobenzene and 4mL of dichloroethane are added into a reactor at room temperature, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into the reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, separating by column chromatography to obtain the p-fluoroaniline, wherein the reaction yield is 54%.
Example 3
The synthetic roadmap is specifically referred to in fig. 4.
The reduction reaction process is specifically as follows: at room temperature, adding 315mg of p-chloronitrobenzene and 4mL of dichloroethane into a reactor, stirring, and adding 1.86g of triethylsilane and 254mg of elemental iodine into a reaction system after dissolution; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the p-chloroaniline is obtained by column chromatography separation, and the reaction yield is 22%.
Example 4
The synthetic roadmap is specifically referred to in fig. 5.
The reduction reaction process is specifically as follows: at room temperature, 404mg of p-bromonitrobenzene and 4mL of dichloroethane are added into a reactor, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into a reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 100 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the p-bromoaniline is obtained by column chromatography separation, and the reaction yield is 41%.
Example 5
The synthetic roadmap is specifically referred to in fig. 6.
The reduction reaction process is specifically as follows: at room temperature, adding 315mg of o-chloronitrobenzene and 4mL of dichloroethane into a reactor, stirring, and adding 1.86g of triethylsilane and 254mg of elemental iodine into a reaction system after dissolution; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, separating by column chromatography to obtain o-chloroaniline, wherein the reaction yield is 75%.
Example 6
The synthetic roadmap is specifically referred to in fig. 7.
The reduction reaction process is specifically as follows: at room temperature, adding 384mg of 3, 4-dichloronitrobenzene and 4mL of dichloroethane into a reactor, stirring, and adding 1.86g of triethylsilane and 254mg of elemental iodine into a reaction system after dissolution; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the 3, 4-dichloroaniline is obtained by column chromatography separation, and the reaction yield is 93 percent.
Example 7
The synthetic roadmap is specifically referred to in fig. 8.
The reduction reaction process is specifically as follows: 274mg of o-nitrotoluene and 4mL of dichloroethane are added into a reactor at room temperature, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into the reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the o-methylaniline is obtained by column chromatography separation, and the reaction yield is 11%.
Example 8
The synthetic roadmap is specifically referred to in fig. 9.
The reduction reaction process is specifically as follows: at room temperature, adding 349mg of 2-chloro-4-nitrotoluene and 4mL of dichloroethane into a reactor, stirring, and adding 1.86g of triethylsilane and 254mg of elemental iodine into a reaction system after dissolution; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction was stopped, 3-chloro-4-methylaniline was obtained by column chromatography, and the reaction yield was 59%.
Example 9
The synthetic roadmap is specifically referred to in fig. 10.
The reduction reaction process is specifically as follows: at room temperature, adding 384mg of 2, 5-dichloronitrobenzene and 4mL of dichloroethane into a reactor, stirring, and adding 1.86g of triethylsilane and 254mg of elemental iodine into a reaction system after dissolution; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the 2, 5-dichloroaniline is obtained by column chromatography separation, and the reaction yield is 70%.
Example 10
The synthetic roadmap is specifically referred to in fig. 11.
The reduction reaction process is specifically as follows: at room temperature, 306mg of paranitroanisole and 4mL of dichloroethane are added into a reactor, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into a reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); after the reaction was stopped, p-methoxyaniline was obtained by column chromatography separation in 71% yield.
Example 11
The synthetic roadmap is specifically referred to in fig. 12.
The reduction reaction process is specifically as follows: 50mg of 4-fluoro-3-nitroaniline and 2mL of dichloroethane are added into a reactor at room temperature, stirred, and 37mg of triethylsilane and 38mg of elemental iodine are added into a reaction system after dissolution; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 150 ℃, and the heating rate is 15 ℃/min); is not reacted.
Example 12
The synthetic roadmap is specifically referred to in fig. 13.
The reduction reaction process is specifically as follows: at room temperature, 312mg of 2-nitro-5-fluoroaniline and 4mL of dichloroethane are added into a reactor, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into a reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 180 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the 4-fluorophenyldiamine is obtained by column chromatography separation, and the reaction yield is 29%.
Example 13
The synthetic roadmap is specifically referred to in fig. 14.
The reduction reaction process is specifically as follows: at room temperature, adding 470mg of 2, 6-difluoro-4-bromonitrobenzene and 4mL of dichloroethane into a reactor, stirring, and adding 1.86g of triethylsilane and 254mg of elemental iodine into a reaction system after dissolution; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 180 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the 2, 6-difluoro-4-bromoaniline is obtained by column chromatography separation, and the reaction yield is 60%.
Example 14
The synthetic roadmap is specifically referred to in fig. 15.
The reduction reaction process is specifically as follows: 470 g of 2-fluoro-4-bromo-6-nitroaniline and 4mL of dichloroethane are added to the reactor at room temperature, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added to the reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 180 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, the 5-bromo-3-fluoro-1, 2-phenylenediamine is obtained by column chromatography separation, and the reaction yield is 88%.
Example 15
The synthetic roadmap is specifically referred to in fig. 16.
The reduction reaction process is specifically as follows: at room temperature, 414mg of 2-nitro-4, 5-dichloroaniline and 4mL of dichloroethane are added into a reactor, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into a reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 180 ℃, and the heating rate is 15 ℃/min); after the reaction is stopped, 4, 5-dichloro o-phenylenediamine is obtained through column chromatography separation, and the reaction yield is 55%.
Example 16
The synthetic route is specifically referred to fig. 17.
The reduction reaction process is specifically as follows: at room temperature, 440mg of 3-fluoro-5-bromonitrobenzene and 4mL of dichloroethane are added into a reactor, stirred, and after dissolution, 1.86g of triethylsilane and 254mg of elemental iodine are added into a reaction system; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 120 ℃, and the heating rate is 5 ℃/min); after the reaction is stopped, the 3-fluoro-5-bromoaniline is obtained by column chromatography separation, and the reaction yield is 85%.
Example 17
The synthetic route is specifically referred to fig. 18.
The reduction reaction process is specifically as follows: at room temperature, adding 460 mg of 2-bromo-5-nitroanisole and 4mL of dichloroethane into a reactor, stirring, and adding 1.86g of triethylsilane and 254mg of elemental iodine into a reaction system after dissolving; after the addition, stirring is continued, sampling GC tracking is carried out (1N NaOH is used for adjusting to be alkaline; the sampling condition is that the initial temperature of a column is 180 ℃, and the heating rate is 15 ℃/min); is not reacted.
In summary, the aromatic nitro compound is used as a raw material, and the aromatic amine compound is obtained by one-step reaction under the conditions of a triethylsilane and iodine simple substance system and room temperature. On the premise of obtaining good yield, the whole steps are simple and convenient to operate, the reaction process is mild, and the preparation is easy.
The foregoing description is only illustrative of the preferred embodiments of the present invention and is not to be construed as limiting the scope of the invention, i.e., the invention is not limited to the specific embodiments described herein, but is intended to cover all modifications and equivalent arrangements included within the scope of the invention.
Claims (6)
1. A preparation method of aromatic amine compounds is characterized in that: aromatic hydrocarbon nitro compound is used as raw material, and aromatic amine compound is obtained by one-step reaction in triethylsilane and iodine simple substance system under the condition of room temperature, and the synthetic route diagram is as follows:
wherein the method comprises the steps ofX, Y, Z may be H, F, cl, br, NH 2 、NO 2 Or OMe.
2. The method for producing an aromatic amine compound according to claim 1, wherein: the reduction reaction process is specifically as follows: at room temperature, adding aromatic nitro compound and solvent into a reactor, stirring, and adding triethylsilane and iodine simple substance into a reaction system after dissolving; after the addition, stirring is continued, and sampling GC tracking is carried out; and after the reaction is stopped, separating by column chromatography to obtain the aromatic amine compound.
3. The method for producing an aromatic amine compound according to claim 2, wherein: the ratio of the amounts of triethylsilane and aromatic nitro compound used in the reduction was 8.0:1.0.
4. the method for producing an aromatic amine compound according to claim 2, wherein: the ratio of the amounts of the substances of the elemental iodine and the aromatic nitro compound used in the reduction reaction was 0.5:1.0.
5. the method for producing an aromatic amine compound according to claim 2, wherein: in the reduction reaction, the solvent is dichloroethane.
6. The method for producing an aromatic amine compound according to claim 2, wherein: during the reduction reaction, the mass ratio of the volume of the solvent to the aromatic hydrocarbon nitro compound is 8.0-15.0mL:1.0g.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311721198.8A CN117820127A (en) | 2023-12-14 | 2023-12-14 | Preparation method of aromatic amine compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311721198.8A CN117820127A (en) | 2023-12-14 | 2023-12-14 | Preparation method of aromatic amine compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117820127A true CN117820127A (en) | 2024-04-05 |
Family
ID=90521920
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311721198.8A Pending CN117820127A (en) | 2023-12-14 | 2023-12-14 | Preparation method of aromatic amine compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117820127A (en) |
-
2023
- 2023-12-14 CN CN202311721198.8A patent/CN117820127A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US20100130788A1 (en) | Method for producing amines | |
| US6140539A (en) | Preparation of amines | |
| US7468461B2 (en) | Method for the production of amines | |
| US2823235A (en) | Hydrogenation of nitro compounds to amines and catalyst therefor | |
| US9505705B2 (en) | Method for producing amines with a catalyst containing platinum, nickel and an additional metal | |
| CN101224422A (en) | SiO2 supported nanometer silver catalyst, preparing method and applications thereof | |
| JP4523275B2 (en) | Supported catalysts for the hydrogenation of nitroaromatic compounds. | |
| US4185036A (en) | Hydrogenation of mixed aromatic nitrobodies | |
| CA1127185A (en) | Toluene diamine from non-washed dinitrotoluene | |
| DE19824906A1 (en) | Conversion of aromatic amines to mono- and dicycloaliphatic amines | |
| CN117820127A (en) | Preparation method of aromatic amine compound | |
| DE19827282A1 (en) | Process for the preparation of cycloaliphatic amines | |
| US3093685A (en) | Catalytic reduction of aromatic mononitro compounds | |
| US6403833B1 (en) | Single step hydrogenation of nitrobenzene to p-aminophenol | |
| US5646085A (en) | Material based on tungsten carbide(s), catalyst and process useful for the hydrogenation of an aromatic nitro or nitroso derivative employing this catalyst | |
| JP3317060B2 (en) | Production method of aromatic amine | |
| GB2044759A (en) | Hydrogenation of aromatic bis - methyl - amines | |
| DE19845641A1 (en) | Process for the preparation of dicycloaliphatic amines | |
| CN112300007B (en) | Catalytic hydrogenation method for 4-nitrodiphenylamine and 4-nitrosodiphenylamine-containing condensate | |
| CN116462597A (en) | Application of iron oxide and copper oxide mixture as catalyst in preparation of p-aminophenol by catalyzing p-nitrophenol | |
| JP3080776B2 (en) | Method for producing 4-alkoxyanilines | |
| CN118108584A (en) | Continuous production method and continuous production system of parahydroxyben-zaldehyde | |
| DE2214056C3 (en) | Catalyst and process for the reduction of nitro compounds | |
| JP2000095740A (en) | Production of n-alkyl substituted aromatic amino compound | |
| JP2000256278A (en) | Production of n-alkyl-substituted aromatic amino compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |