CN115960056A - Novel method for synthesizing para-substituted aniline compound - Google Patents

Novel method for synthesizing para-substituted aniline compound Download PDF

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CN115960056A
CN115960056A CN202111194690.5A CN202111194690A CN115960056A CN 115960056 A CN115960056 A CN 115960056A CN 202111194690 A CN202111194690 A CN 202111194690A CN 115960056 A CN115960056 A CN 115960056A
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trifluoromethanesulfonimide
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魏邦国
聂晓迪
毛卓亚
郭家明
司长梅
林国强
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Fudan University
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Abstract

The invention belongs to the technical field of chemical synthesis, relates to a preparation method for synthesizing para-substituted aniline compounds, and particularly relates to a novel preparation method for synthesizing para-substituted aniline compounds 1 and 2. The method can synthesize a series of para-substituted aniline compounds efficiently and regioselectively, can perform later modification on active biomolecules, and can provide a key way for constructing organic synthetic building blocks. Meanwhile, the method can conveniently realize gram-grade preparation in a laboratory, and is suitable for large-scale production.

Description

Novel method for synthesizing para-substituted aniline compound
Technical Field
The invention belongs to the technical field of chemical synthesis, relates to a preparation method for synthesizing a para-substituted aniline compound, and particularly relates to a new preparation method for synthesizing para-substituted aniline compounds 1 and 2.
Background
The prior art discloses that an aniline structure is a relatively common structure in modern commercial drug molecules, such as Fentanyl (Fentanyl) which is a clinical analgesic anesthetic, chlorambucil (chlorembuil) which is an anti-tumor drug for treating chronic lymphocytic leukemia, ovarian cancer and low-grade non-hodgkin lymphoma, nefazodone (Nefazodone) which is an anti-depression drug, lidocaine (Lidocaine) which is an anti-arrhythmia drug, lenalidomide (lenalidomide) which is an anti-tumor and immunoregulatory drug, mefenamic acid (Mefenamic acid), and structures of aniline and analogues thereof (shown in the following formula (I)). In addition, aniline compounds are also widely used in agriculture and are key active ingredients of several agricultural chemicals, such as the broad-spectrum herbicide Flumetsulam (Flumetsulam), chloracetanilide herbicide (metacochlor), the effective broad-spectrum bactericide Iprodione (Iprodione) of the dicarboximide class, and the antiparasitic agent fluzosulfuron (Fluazuron).
Figure BDA0003302571370000021
The part of formula (A) comprises active molecules of aniline and derivatives thereof
In conclusion, aniline derivatives substituted at different positions have unique advantages in the field of medicinal chemistry. However, how to regioselectively perform aniline functionalization has been one of the major concerns and difficulties for organic synthetic chemists. The aniline functionalization with high regioselectivity can not only carry out later modification on active biomolecules, but also provide a key way for the construction of organic synthetic building blocks. Therefore, the research on the fast and efficient regioselective synthesis methodology of the aniline derivatives is of great significance.
Based on the current situation of the prior art, the inventor of the application intends to provide a preparation method for synthesizing the para-substituted aniline compound, and particularly relates to a new preparation method for synthesizing the para-substituted aniline compounds 1 and 2.
Disclosure of Invention
The invention aims to provide a preparation method for synthesizing a para-substituted aniline compound based on the current situation of the prior art, and particularly relates to a novel preparation method for synthesizing para-substituted aniline compounds 1 and 2.
The technical route of the preparation method of the para-position substituted tertiary amine compounds 1 and 2 aims at preparing the para-position substituted tertiary amine compound with high efficiency, low cost, high regioselectivity and amplification, and is a simple and convenient process technical route.
The technical route for the preparation of para-substituted tertiary amine compounds 1 and 2 according to the invention is as follows, and in the examples set out below, the general formula of the intermediates is indicated by Arabic numerals according to the numbering in the formula.
Figure BDA0003302571370000031
Wherein R is 1 Refers to methyl, ethyl, n-butyl, allyl, cyclohexyl, benzyl, 3-methylbenzyl, 3-fluorobenzyl, 3-chlorobenzyl, 3-trifluoromethylbenzyl, 4-tert-butylbenzyl, 4-bromobenzyl, 4-isopropylbenzyl; r is 2 Refers to methyl, ethyl, n-butyl, allyl, cyclopropyl, cyclohexyl, benzyl, 3-methylbenzyl, 3-fluorobenzyl, 3-chlorobenzyl, 3-trifluoromethylbenzyl, 4-tert-butylbenzyl, 4-bromobenzyl, 4-isopropylbenzyl; r 3 Is phenyl, 2-bromophenyl, 2-trifluoromethylphenyl, 2-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-methoxyphenyl; r 4 Refers to benzyl; r is 5 The structural formula refers to ester group, p-toluenesulfonyl, p-methylsulfonyl and 4-chlorobenzenesulfonyl, and the structure is shown in detail. Syntheses of compounds 2 and 3 were prepared according to literature procedures, see in particular literature (j.org.chem.2021, 86,1901-1910.j.org.chem.2019,84, 914-923).
Step 1: dissolving the compound 3 and the compound 4in an organic solvent, adding a Lewis acid, reacting for 4-8 hours at room temperature or in a reflux state, adding a saturated solution of sodium bicarbonate for quenching, and carrying out aftertreatment to obtain the compound 1 or 2. Wherein one Lewis acid is bis (trifluoromethanesulfonimide) silver, bis (trifluoromethanesulfonimide) calcium, tris (pentafluorophenyl) borane, particularly bis (trifluoromethanesulfonimide) silver, and one organic solvent is chloroform, carbon tetrachloride, hexafluoro-2-propanol, toluene, 1, 2-dichloroethane, etc., particularly trichloromethane and hexafluoro-2-propanol.
The para-substituted aniline compound synthesized by the invention has a chemical structure shown in a formula (I):
Figure BDA0003302571370000041
wherein R is 1 Refers to methyl, ethyl, n-butyl, allyl, cyclohexyl, benzyl, 3-methylbenzyl, 3-fluorobenzyl, 3-chlorobenzyl, 3-trifluoromethylbenzyl, 4-tert-butylbenzyl, 4-bromobenzyl, 4-isopropylbenzyl; r is 2 Refers to methyl, ethyl, n-butyl, allyl, cyclopropyl, cyclohexyl, benzyl, 3-methylbenzyl, 3-fluorobenzyl, 3-chlorobenzyl, 3-trifluoromethylbenzyl, 4-tert-butylbenzyl, 4-bromobenzyl, 4-isopropylbenzyl; r 3 Is phenyl, 2-bromophenyl, 2-trifluoromethylphenyl, 2-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-methoxyphenyl; r is 4 Refers to benzyl; r 5 The structure refers to ester group, p-toluenesulfonyl, p-methylsulfonyl and 4-chlorobenzenesulfonyl.
Further, the specific chemical structure of the para-substituted aniline compound is as follows:
Figure BDA0003302571370000051
the method for preparing the para-substituted aniline compound has the advantages of mild conditions, simple operation, good yield, excellent chemical selectivity and regioselectivity, and common reagents, and can be used for gram-scale preparation.
Detailed Description
Example 1
Dissolving the compound 3 and the compound 4in trichloromethane, adding bis (trifluoromethanesulfonimide) silver, reacting for 4 hours under a reflux state, adding a saturated solution of sodium bicarbonate for quenching, and performing post-treatment to obtain the compound 1 or 2.
Compound 1a
Yellow oil (107mg, 70%). E/Z = 61. 1 H NMR(400MHz,CDCl 3 )δ7.78(d,J＝8.0Hz,2H,major),7.40(d,J＝8.0Hz,1.2H,minor),7.29-7.27(m,1.2H,minor),7.27-7.25(m,2H,major),7.25-7.24(m,1H,major),7.24-7.23(m,0.6H,minor),7.23-7.18(m,3H,minor),7.18-7.14(m,5H,major),7.12-7.09(m,1.2H,minor),7.08-7.05(m,1.2H,minor),7.05-7.03(m,1.2H,minor),7.00-6.97(m,2H,major),6.91(d,J＝7.2Hz,2H,major),6.72(d,J＝8.4Hz,2H,major),6.54(s,0.6H,minor),6.38(s,1H,major),6.34(d,J＝8.4Hz,1.2H,minor),6.27(d,J＝8.4Hz,2H,major),4.53(s,2H,major),4.52-4.40(m,1.2H,minor),3.28-3.22(m,4H,major),3.22-3.19(m,2.4H,minor),2.42(s,3H,major),2.37(s,1.5H,minor),2.00-1.95(m,4H,major),1.95-1.92(m,2.4H,minor)ppm；
Compound 1b
Yellow oil (158mg, 90%). E/Z = 53. 1 H NMR(400MHz,CDCl 3 )δ7.80(d,J＝8.0Hz,2H,major),7.55-7.52(m,0.88H,minor),7.46-7.43(m,0.88H,minor),7.38(d,J＝8.0Hz,2H,major),7.30(d,J＝8.0Hz,1.76H,minor),7.28-7.25(m,1.76H,minor),7.25-7.23(m,3H,major),7.23-7.21(m,2.64H,minor),7.20-7.17(m,1.76H,minor),7.11(d,J＝8.0Hz,2H,major),7.09-7.06(m,1.76H,minor),7.05-7.01(m,2H,major),6.97-6.93(m,2H,major),6.93-6.89(m,1.76H,minor),6.77(d,J＝8.0Hz,2H,major),6.56(s,1H,major),6.34(d,J＝8.4Hz,1.76H,minor),6.30(s,0.88H,minor),6.25(d,J＝8.4Hz,2H,major),4.56(s,2H,major),4.48-4.32(m,1.76H,minor),3.30-3.25(m,3.52H,minor),3.24-3.18(m,4H,major),2.44(s,2.64H,minor),2.39(s,3H,major),2.03-1.99(m,3.52H,minor),1.97-1.93(m,4H,major)ppm；
Compound 1c
Yellow oil (149mg, 86%). 1 H NMR(400MHz,CDCl 3 )δ7.75(d,J＝8.0Hz,2H,major),7.62-7.59(m,0.67H,minor),7.54-7.51(m,0.67H,minor),7.43-7.40(m,0.67H,minor),7.34-7.30(m,2H,major),7.30-7.29(m,0.67H,minor),7.29-7.28(m,1.34H,minor),7.27-7.25(m,2H,major),7.24-7.22(m,3H,major),7.22-7.20(m,1.34H,minor),7.18-7.14(m,2H,major),7.14-7.11(m,1.34H,minor),7.11-7.09(m,1.34H,minor)，7.08-7.05(m,2H,major),6.89-6.87(m,2H,major),6.77(d,J＝8.4Hz,2H,major),6.72-6.70(m,0.67H,minor),6.48-6.44(m,1H,major),6.31(d,J＝8.8Hz,1.34H,minor),6.25(d,J＝8.4Hz,2H,major),4.55(s,2H,major),4.44(s,1.34H,minor),3.27-3.24(m,2.68H,minor),3.23-3.18(m,4H,major),2.42(s,3H,major),2.36(s,2.01H,minor),2.02-1.98(m,2.68H,minor),1.97-1.92(m,4H,major)ppm；
Compound 1d
Yellow oil (86mg, 53%). 1 H NMR(400MHz,CDCl 3 )δ7.83(d,J＝8.0Hz,1.04H,minor),7.44(d,J＝8.0Hz,2H,major),7.34-7.31(m,1.56H,minor),7.31-7.28(m,3H,major),7.28-7.24(m,1.04H,minor),7.24-7.21(m,2H,major),7.21-7.20(m,1.04H,minor),7.20-7.18(m,1.04H,minor),7.16-7.12(m,2H,major),7.08-7.05(m,2H,major),6.96(d,J＝8.4Hz,2H,major),6.86(d,J＝8.0Hz,1.04H,minor),6.82-6.79(m,2H,major),6.78-6.74(m,1.04H,minor),6.71(s,1H,major),6.48(s,0.52H,minor),6.35(d,J＝8.4Hz,2H,major),6.28(d,J＝8.4Hz,1.04H,minor),4.58(s,2H,major),4.52-4.37(m,1.04H,minor),3.83(s,3H,major),3.74(s,1.56H,minor),3.31-3.27(m,4H,major),3.25-3.21(m,2.08H,minor),2.48(s,1.56H,minor),2.43(s,3H,major),2.05-2.00(m,4H,major),1.99-1.96(m,2.08H,minor)ppm；
Compound 1e
Yellow oil (118mg, 75%). E/Z = 52. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.4Hz,1.64H,minor),7.41(d,J＝8.4Hz,2H,major),7.29(d,J＝8.0Hz,2H,major),7.27-7.24(m,1.64H,minor),7.21-7.18(m,3H,major),7.18-7.16(m,1.64H,minor),7.13(d,J＝8.0Hz,2H,major),7.09-7.04(m,2.46H,minor),7.03-7.01(m,1.64H,minor),7.01-6.99(m,2H,major),6.89-6.84(m,1.64H,minor),6.84-6.80(m,2H,major),6.79-6.73(m,2H,major),6.68(d,J＝8.8Hz,1.64H,minor),6.51(s,1H,major),6.37(d,J＝8.8Hz,2H,major),6.34(s,0.82H,minor),6.28(d,J＝8.8Hz,1.64H,minor),4.51(s,2H,major),4.50-4.49(m,1.64H,minor),3.29-3.25(m,4H,major),3.25-3.21(m,3.28H,minor),2.44(s,2.46H,minor),2.40(s,3H,major),2.01-1.98(m,4H,major),1.98-1.95(m,3.28H,minor)ppm；
Compound 1f
Yellow oil (112mg, 69%). E/Z = 65. 1 H NMR(400MHz,CDCl 3 )δ7.76(d,J＝8.4Hz,1H,minor),7.40(d,J＝8.4Hz,2H,major),7.30-7.27(m,1H,major),7.27-7.25(m,0.5H,minor),7.24-7.23(m,0.5H,minor),7.22-7.21(m,0.5H,minor),7.21-7.20(m,1H,major),7.20-7.19(m,1H,major),7.19-7.18(m,1H,minor),7.18-7.16(m,1H,minor),7.12(d,J＝8.0Hz,2H,major),7.08-7.07(m,1H,minor),7.06-7.04(m,2H,major),7.04-7.03(m,2H,major),7.02-7.00(m,2H,major),6.95(d,J＝8.4Hz,2H,major),6.81(d,J＝8.4Hz,1H,minor),6.67(d,J＝8.8Hz,1H,minor),6.50(s,1H,major),6.39(d,J＝8.8Hz,2H,major),6.33(s,0.5H,minor),6.28(d,J＝8.8Hz,1H,minor),4.58-4.52(m,1H,minor),4.51(s,2H,major),3.29-3.26(m,4H,major),3.25-3.22(m,2H,minor),2.44(s,1.5H,minor),2.41(s,3H,major),2.02-1.99(m,4H,major),1.99-1.96(m,2H,minor)ppm；
Compound 1g
White solid (137mg, 78%). E/Z = 52. 1 H NMR(400MHz,CDCl 3 )δ7.76(d,J＝8.4Hz,1.60H,minor),7.39(d,J＝8.4Hz,2H,major),7.28(d,J＝8.0Hz,2H,major),7.26-7.24(m,1.60H,minor),7.22-7.20(m,1.60H,minor),7.20-7.19(m,1.60H,minor),7.19-7.17(m,3H,minor),7.17-7.15(m,2.40H,minor),7.12(d,J＝8.0Hz,2H,major),7.07(d,J＝8.8Hz,2H,major),7.02-6.98(m,2H,major),6.87(d,J＝8.4Hz,2H,major),6.75(d,J＝8.4Hz,1.60H,minor),6.68(d,J＝8.8Hz,1.60H,minor),6.48(s,1H,major),6.40(d,J＝8.8Hz,2H,major),6.31(s,0.80H,minor),6.28(d,J＝8.8Hz,1.60H,minor),4.58-4.51(m,1.60H,minor),4.51(s,2H,major),3.30-3.26(m,4H,major),3.25-3.21(m,3.20H,minor),2.44(s,2.40H,minor),2.41(s,3H,major),2.02-1.99(m,4H,major),1.98-1.95(m,3.20H,minor)ppm；
Compound 1h
Yellow oil (106mg, 68%). E/Z = 66. 1 H NMR(400MHz,CDCl 3 )δ7.83(d,J＝8.0Hz,2H,major),7.49(d,J＝8.0Hz,1.2H,minor),7.35-7.31(m,3H,major),7.31-7.28(m,1.8H,minor),7.27-7.25(m,2H,major),7.24-7.21(m,1.2H,minor),7.19-7.16(m,1.2H,minor),7.14-7.11(m,1.2H,minor),7.10-7.07(m,1.2H,minor),7.06-7.03(m,1.2H,minor),7.03-6.99(m,2H,major),6.94(d,J＝8.0Hz,2H,major),6.87(d,J＝8.0Hz,2H,major),6.79(d,J＝8.4Hz,2H,major),6.57(s,0.6H,minor),6.41-6.39(m,1.2H,minor),6.38(s,1H,major),6.34(d,J＝8.4Hz,2H,major),4.57(s,2H,major),4.57-4.48(m,1.2H,minor),3.34-3.29(m,4H,major),3.29-3.26(m,2.4H,minor),2.49(s,3H,major),2.45(s,1.8H,minor),2.37(s,1.8H,minor),2.28(s,3H,major),2.07-2.02(m,4H,major),2.02-2.00(m,2.4H,minor)ppm；
Compound 1i
Yellow oil (116mg, 72%). E/Z = 69. 1 H NMR(400MHz,CDCl 3 )δ7.70(d,J＝8.0Hz,2H,major),7.45(d,J＝8.4Hz,0.94H,minor),7.30-7.27(m,2H,major),7.27-7.25(m,0.94H,minor),7.25-7.23(m,2H,major),7.21-7.20(m,0.94H,minor),7.20-7.18(m,2H,major),7.17-7.16(m,0.94H,minor),7.14-7.13(m,1H,major),7.12-7.11(m,0.47H,minor),7.05-7.02(m,0.94H,minor),6.93(d,J＝8.8Hz,0.94H,minor),6.85(d,J＝8.4Hz,2H,major),6.75-6.72(m,2H,major),6.72-6.70(m,0.94H,minor),6.65-6.60(m,2H,major),6.49(s,0.47H,minor),6.34-6.32(m,0.94H,minor),6.31-6.29(m,2H,major),6.29(s,1H,major),4.57-4.51(m,0.94H,minor),4.50(s,2H,major),3.79(s,1.42H,minor),3.71(s,3H,major),3.26-3.24(m,4H,major),3.23-3.22(m,1.88H,minor),2.44(s,3H,major),2.39(s,1.42H,minor),2.01-1.97(m,4H,major),1.97-1.94(m,1.88H,minor)ppm；
Compound 1j
White solid (67mg, 52%). E/Z>20:1. 1 H NMR(400MHz,CDCl 3 )δ7.36-7.34(m,2H),7.31-7.28(m,2H),7.28-7.26(m,1H),7.25-7.23(m,3H),7.21-7.16(m,3H),6.55(s,1H),6.49(d,J＝8.8Hz,2H),4.65-4.40(m,2H),3.32-3.26(m,4H),2.46(s,3H),2.04-1.97(m,4H)ppm；
Compound 2a
Yellow oil (128mg, 81%). E/Z = 63. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.4Hz,1H,minor),7.43(d,J＝8.4Hz,1H,minor),7.33-7.30(m,2H,major),7.28-7.25(m,2H,major),7.24-7.23(m,2H,major),7.23-7.22(m,1H,minor),7.22-7.21(m,2.5H,minor),7.20-7.19(m,5H,major),7.11-7.07(m,1.5H,minor),7.07-7.03(m,3H,major),6.93(d,J＝8.4Hz,2H,major),6.76(d,J＝8.4Hz,1H,minor),6.55(s,1H,major),6.34-6.31(m,2H,major),6.31-6.30(m,1H,minor),6.29(s,0.5H,minor),4.55(s,2H,major),4.52-4.42(m,1H,minor),3.28-3.26(m,4H,major),3.25-3.22(m,2H,minor),2.03-2.00(m,4H,major),1.99-1.97(m,2H,minor)ppm；
Compound 2b
White solid (111mg, 63%). E/Z>20:1.mp 151-153℃. 1 H NMR(400MHz,CDCl 3 )δ7.40(d,J＝8.0Hz,2H),7.26-7.22(m,2H),7.12-7.18(m,4H),7.12(d,J＝8.4Hz,2H),7.10-7.06(m,2H),7.05-6.99(m,2H),6.75(d,J＝2.4Hz,1H),6.56-6.53(m,1H),6.52(s,1H),6.16(dd,J＝8.8,2.4Hz,1H),4.44-4.35(m,2H),3.28-3.20(m,4H),2.39(s,3H),2.05-1.96(m,4H)ppm；
Compound 2c
Yellow oil (88mg, 61%). E/Z = 80. 1 H NMR(400MHz,CDCl 3 )δ7.78(d,J＝8.0Hz,0.4H,minor),7.39(d,J＝8.0Hz,2H,major),7.29(d,J＝8.0Hz,2H,minor),7.28-7.24(m,1H,major),7.21-7.19(m,3H,major),7.19-7.16(m,5H,major),7.16-7.14(m,0.6H,minor),7.12(d,J＝8.0Hz,2H,major),7.09-7.06(m,0.4H,minor),7.01-6.97(m,4H,major),6.90(d,J＝7.2Hz,0.4H,minor),6.73(d,J＝8.4Hz,0.4H,minor),6.55(s,1H,major),6.50(d,J＝8.8Hz,2H,major),6.43(d,J＝8.4Hz,0.4H,minor),6.39(s,0.2H,minor),4.52(s,2H,major),4.42-4.40(m,0.4H,minor),2.94(s,6H,major),2.92(s,1.2H,minor),2.45(s,0.6H,minor),2.40(s,3H,major)ppm；
Compound 2d
Yellow oil (101mg, 68%). E/Z = 51. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.0Hz,1.7H,minor),7.37(d,J＝8.0Hz,2H,major),7.30-7.27(m,2H,major),7.26-7.23(m,1.7H,minor),7.21-7.19(m,5H,major),7.19-7.17(m,4.25H,minor),7.11-7.08(m,2H,major),7.07-7.04(m,1.7H,minor),7.02-6.99(m,2H,major),6.98-6.95(m,2H,major),6.93-6.89(m,1.7H,minor),6.74-6.69(m,1.7H,minor),6.55(s,1H,major),6.49-6.45(m,2H,major),6.37(s,0.85H,minor),4.59-4.52(m,2H,major),4.52-4.36(m,1.7H,minor),3.40-3.36(m,1.7H,minor),3.36-3.31(m,2H,major),2.89(s,3H,major),2.86(s,2.55H,minor),2.44(s,2.55H,minor),2.38(s,3H,major),1.13-1.10(m,3H,major),1.09-1.07(m,2.55H,minor)ppm；
Compound 2e
Yellow oil (101mg, 66%). E/Z = 57. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.4Hz,1.65H,minor),7.36(d,J＝8.4Hz,2H,major),7.31-7.28(m,1.65H,minor),7.26-7.24(m,2H,major),7.21-7.19(m,4.13H,minor),7.19-7.16(m,5H,major),7.12-7.09(m,2H,major),7.08-7.04(m,2H,major),7.01-6.98(m,1.65H,minor),6.97(d,J＝8.8Hz,2H,major),6.91-6.88(m,1.65H,minor),6.72(d,J＝8.8Hz,1.65H,minor),6.55(s,1H,major),6.48(d,J＝8.8Hz,2H,major),6.42(d,J＝9.2Hz,1.65H,minor),6.37(s,0.82H,minor),5.87-5.80(m,1H,major),5.80-5.74(m,0.82H,minor),5.18-5.14(m,2H,major),5.14-5.09(m,1.65H,minor),4.52(s,2H,major),4.52-4.38(m,1.65H,minor),3.92-3.89(m,1.65H,minor),3.89-3.84(m,2H,major),2.93(s,3H,major),2.89(s,2.5H,minor),2.45(s,2.50H,minor),2.39(s,3H,major)ppm；
Compound 2f
Yellow oil (142mg, 85%). E/Z = 69. 1 H NMR(400MHz,CDCl 3 )δ7.76(d,J＝8.4Hz,2H,major),7.37-7.35(m,0.95H,minor),7.35-7.33(m,2H,major),7.32-7.31(m,0.95H,minor),7.30-7.28(m,2H,major),7.27-7.26(m,2H,major),7.25-7.24(m,2.35H,minor),7.23-7.22(m,0.95H,minor),7.22-7.21(m,0.95H,minor),7.19-7.18(m,5H,major),7.17-7.16(m,0.95H,minor),7.08-7.07(m,0.95H,minor),7.07-7.06(m,0.95H,minor),7.06-7.04(m,2H,major),7.00-6.98(m,0.95H,minor),6.97-6.94(m,2H,major),6.91-6.87(m,2H,major),6.71(d,J＝8.8Hz,2H,major),6.55(s,0.47H,minor),6.52(d,J＝9.2Hz,0.95H,minor),6.46(d,J＝9.2Hz,2H,major),6.38(s,1H,major),4.55-4.51(m,4H,major),4.50-4.48(m,2H,minor),3.02(s,1.41H,minor),2.97(s,3H,major),2.44(s,3H,major),2.36(s,1.41H,minor)ppm；
Compound 2g
Yellow oil (165mg, 96%). E/Z = 57. 1 H NMR(400MHz,CDCl 3 )δ7.75(d,J＝8.4Hz,1.3H,minor),7.36-7.33(m,2H,major),7.32-7.31(m,2H,major),7.30-7.28(m,1.3H,minor),7.28-7.25(m,2H,major),7.25-7.24(m,1.3H,minor),7.24-7.22(m,1.95H,minor),7.22-7.21(m,1.3H,minor),7.21-7.20(m,3.25H,minor),7.19-7.17(m,5H,major),7.17-7.16(m,2H,major),7.16-7.14(m,1.3H,minor),7.07-7.05(m,1.3H,minor),7.05-7.03(m,2H,major),7.00-6.97(m,2H,major),6.95-6.91(m,2H,major),6.91-6.86(m,1.3H,minor),6.70(d,J＝8.8Hz,1.3H,minor),6.53(s,1H,major),6.45(d,J＝8.8Hz,2H,major),6.40(d,J＝8.8Hz,1.3H,minor),6.35(s,0.65H,minor),4.53(s,2H,major),4.50(s,2H,major),4.49-4.47(m,1.3H,minor),4.46(s,1.3H,minor),3.51-3.44(m,1.3H,minor),3.44-3.35(m,2H,major),2.42(s,1.95H,minor),2.34(s,3H,major),1.22-1.17(m,3H,major),1.17-1.13(m,1.95H,minor)ppm；
Compound 2h
Yellow oil (139mg, 79%). E/Z = 69. 1 H NMR(400MHz,CDCl 3 )δ7.74(d,J＝8.0Hz,0.8H,minor),7.34-7.33(m,2H,major),7.33-7.32(m,2H,major),7.31-7.28(m,0.8H,minor),7.28-7.27(m,2H,major),7.27-7.23(m,4H,major),7.20-7.18(m,5H,major),7.18-7.17(m,1.6H,minor),7.17-7.15(m,2H,major),7.15-7.13(m,0.8H,minor),7.07-7.05(m,0.8H,minor),7.05-7.03(m,2H,major),6.96(d,J＝6.8Hz,2H,major),6.91(d,J＝6.8Hz,2H,major),6.89-6.87(m,0.8H,minor),6.68(d,J＝8.8Hz,0.8H,minor),6.52(s,1H,major),6.47(d,J＝8.8Hz,2H,major),6.40(d,J＝8.8Hz,0.8H,minor),6.33(s,0.4H,minor),4.52(s,2H,major),4.45-4.41(m,0.8H,minor),4.40(s,2H,major),4.38(s,0.8H,minor),4.27-4.23(m,1H,major),4.22-4.18(m,0.4H,minor),2.42(s,1.2H,minor),2.36(s,3H,major),1.22-1.19(m,6H,major),1.18-1.16(m,2.4H,minor)ppm；
Compound 2i
Yellow oil (135mg, 72%, PE/EA = 15) — E/Z = 63. 1 HNMR(400MHz,CDCl 3 )δ7.74(d,J＝8.0Hz,1.1H,minor),7.34-7.32(m,2H,major),7.32-7.30(m,2H,major),7.30-7.27(m,1.1H,minor),7.27-7.24(m,4H,major),7.24-7.22(m,2.2H,minor),7.22-7.20(m,2H,major),7.19-7.18(m,5H,major),7.18-7.16(m,2.75H,minor),7.16-7.15(m,1.1H,minor),7.06-7.04(m,2H,major),7.04-7.02(m,1.1H,minor),6.99-6.96(m,2H,major),6.91(d,J＝8.8Hz,2H,major),6.90-6.88(m,1.1H,minor),6.69(d,J＝8.8Hz,1.1H,minor),6.52(s,1H,major),6.45(d,J＝8.8Hz,2H,major),6.39(d,J＝9.2Hz,1.1H,minor),6.32(s,0.55H,minor),4.65-4.52(m,1.1H,minor),4.52(s,1.1H,minor),4.45(s,2H,major),4.42(s,2H,major),3.78-3.73(m,1H,major),3.72-3.65(m,0.55H,minor),2.42(s,1.65H,minor),2.35(s,3H,major),1.91-1.84(m,4H,major),1.82-1.77(m,2.2H,minor),1.71-1.67(m,1H,major),1.67-1.63(m,0.55H,minor),1.39-1.35(m,4H,major),1.34-1.33(m,1H,major),1.32-1.30(m,0.55H,minor),1.17-1.03(m,2.2H,minor)ppm；
Compound 2j
Yellow oil (84mg, 55%). E/Z = 64. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.0Hz,1H,minor),7.36(d,J＝8.4Hz,2H,major),7.31-7.28(m,1H,minor),7.27-7.24(m,2.5H,minor),7.21-7.19(m,2H,major),7.19-7.18(m,5H,major),7.10(d,J＝7.6Hz,2H,major),7.09-7.05(m,1H,minor),7.04-7.00(m,2H,major),6.95(d,J＝8.8Hz,2H,major),6.93-6.89(m,1H,minor),6.72(d,J＝8.8Hz,1H,minor),6.53(s,1H,major),6.43(d,J＝8.8Hz,2H,major),6..38(d,J＝8.8Hz,1H,minor),6.33(s,0.5H,minor),4.54(s,2H,major),4.51-4.38(m,1H,minor),3.39-3.31(m,4H,major),3.31-3.25(m,2H,minor),2.45(s,1.5H,minor),2.39(s,3H,major),1.19-1.14(m,6H,major),1.14-1.10(m,3H,minor)ppm；
Compound 2k
Yellow oil (142mg, 83%). E/Z = 60. 1 H NMR(400MHz,CDCl 3 )δ7.82(d,J＝8.0Hz,1.3H,minor),7.40(d,J＝8.4Hz,2H,major),7.32(d,J＝8.0Hz,2H,major),7.31-7.30(m,1.3H,minor),7.30-7.29(m,0.65H,minor),7.29-7.28(m,1H,major),7.25-7.24(m,5H,major),7.24-7.23(m,3.25H,minor),7.22-7.21(m,2H,major),7.21-7.19(m,1.3H,minor),7.14-7.11(m,4H,major),7.10-7.06(m,2.6H,minor),7.05-7.02(m,2H,major),7.02-6.98(m,2H,major),6.95-6.93(m,1.3H,minor),6.75(d,J＝9.2Hz,1.3H,minor),6.59(s,1H,major),6.51(d,J＝9.2Hz,2H,major),6.46(s,0.65H,minor),6.44-6.42(m,1.3H,minor),4.57(s,2H,major),4.57-4.51(m,1.3H,minor),4.49(s,1.3H,minor),4.47(s,2H,major),3.08(s,3H,major),3.03(s,2H,minor),2.48(s,2H,minor),2.40(s,3H,major),2.36(s,3H,major),2.32(s,2H,minor)ppm；
Compound 2l
Yellow oil (170mg, 98%). E/Z = 70. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.4Hz,2H,major),7.36(d,J＝8.0Hz,0.80H,minor),7.30-7.26(m,3H,major),7.26-7.25(m,1.20H,minor),7.25-7.23(m,2H,minor),7.21-7.17(m,5H,major),7.10-7.08(m,0.80H,minor),7.08-7.06(m,2H,major),7.06-7.04(m,0.80H,minor),7.00-6.98(m,0.80H,minor),6.98-6.95(m,2H,major),6.95-6.90(m,2H,major),6.90-6.87(m,2H,major),6.87-6.83(m,0.80H,minor),6.72(d,J＝8.8Hz,2H,major),6.55(s,0.40H,minor),6.49(d,J＝9.2Hz,0.80H,minor),6.43(d,J＝8.8Hz,2H,major),6.38(s,1H,major),4.53(s,2H,major),4.52-4.50(m,0.80H,minor),4.50-4.47(m,0.80H,minor),4.47(s,2H,major),3.02(s,1.20H,minor),2.97(s,3H,major),2.43(s,3H,major),2.36(s,1.20H,minor)ppm；
Compound 2m
Yellow oil (171mg, 96%). E/Z = 76. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.4Hz,2H,major),7.35(d,J＝8.4Hz,0.66H,minor),7.29(d,J＝8.0Hz,2H,major),7.27-7.26(m,0.66H,minor),7.25-7.23(m,3H,major),7.23-7.22(m,0.99H,minor),7.21-7.18(m,5H,major),7.17-7.14(m,1.65H,minor),7.10-7.08(m,1.32H,minor),7.08-7.03(m,4H,major),7.00-6.97(m,0.66H,minor),6.97-6.95(m,0.66H,minor),6.91-6.86(m,2H,major),6.73-6.68(m,2H,major),6.55(s,0.33H,minor),6.48(d,J＝8.8Hz,0.66H,minor),6.43(d,J＝8.8Hz,2H,major),6.38(s,1H,major),4.53(s,2H,major),4.52-4.49(m,0.66H,minor),4.48(s,0.66H,minor),4.45(s,2H,major),3.02(s,3H,major),2.97(s,0.99H,minor),2.44(s,3H,major),2.36(s,0.99H,minor)ppm；
Compound 2n
Yellow oil (184mg, 98%). E/Z = 67. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.0Hz,1H,minor),7.54-7.50(m,1H,minor),7.50-7.44(m,2H,major),7.44-7.39(m,2H,major),7.39-7.33(m,3H,major),7.29-7.25(m,1.5H,minor),7.25-7.23(m,1H,major),7.23-7.21(m,0.5H,minor),7.21-7.18(m,5H,major),7.18-7.17(m,2.5H,minor),7.17-7.15(m,1H,major),7.10-7.08(m,1H,minor),7.08-7.07(m,0.5H,minor),7.07-7.04(m,2H,major),7.01-6.98(m,2H,major),6.98-6.95(m,2H,major),6.90-6.86(m,1H,minor),6.75-6.71(m,1H,minor),6.56(s,1H,major),6.51(d,J＝8.8Hz,2H,major),6.44(d,J＝8.8Hz,1H,minor),6.38(s,0.5H,minor),4.55(s,2H,major),4.52(s,2H,major),,4.52(s,1H,minor),4.48-4.36(m,1H,minor),3.01(s,3H,major),2.97(s,1.5H,minor),2.43(s,1.5H,minor),2.35(s,3H,major)ppm；
Compound 2o
Yellow oil (124mg, 67%). E/Z = 66. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.0Hz,2H,major),7.38-7.36(m,1H,minor),7.36-7.34(m,2H,major),7.33-7.32(m,1H,minor),7.30-7.27(m,2H,major),7.27-7.26(m,1H,minor),7.26-7.24(m,2.5H,minor),7.21-7.19(m,5H,major),7.19-7.16(m,2H,major),7.16-7.14(m,1H,minor),7.13-7.11(m,1.5H,minor),7.08-7.05(m,3H,major),6.99-6.97(m,1H,minor),6.96-6.94(m,1H,minor),6.92-6.87(m,2H,major),6.72-6.67(m,2H,major),6.55(s,0.5H,minor),6.52(d,J＝9.2Hz,1H,minor),6.46(d,J＝8.8Hz,2H,major),6.37(s,1H,major),4.53(s,2H,major),4.52-4.50(m,1H,minor),4.50(s,1H,minor),4.47(s,2H,major),3.01(s,1.5H,minor),2.96(s,3H,major),2.44(s,3H,major),2.36(s,1.5H,minor),1.32(s,4.5H,minor),1.31(s,9H,major)ppm；
Compound 2p
Yellow oil (187mg, 98%). E/Z = 73. 1 H NMR(400MHz,CDCl 3 )δ7.76(d,J＝8.0Hz,2H,major),7.45-7.43(m,0.88H,minor),7.43-7.40(m,2H,major),7.36(d,J＝8.0Hz,0.88H,minor),7.27(d,J＝8.0Hz,2H,major),7.26-7.24(m,0.88H,minor),7.24-7.22(m,2.20H,minor),7.19-7.17(m,5H,major),7.11-7.05(m,5H,major),7.05-7.02(m,2.20H,minor),6.97(d,J＝8.0Hz,2H,major),6.90-6.88(m,0.88H,minor),6.88-6.86(m,0.88H,minor),6.73(d,J＝8.8Hz,2H,major),6.54(s,0.44H,minor),6.49(d,J＝8.8Hz,0.88H,minor),6.43(d,J＝8.8Hz,2H,major),6.36(s,1H,major),4.52(s,2H,major),4.51-4.45(m,0.88H,minor),4.45-4.43(m,0.88H,minor),4.41(s,2H,major),2.99(s,1.32H,minor),2.94(s,3H,major),2.43(s,3H,major),2.36(s,1.32H,minor)ppm；
Compound 2q
Yellow oil (112mg, 62%). E/Z = 58. 1 H NMR(400MHz,CDCl 3 )δ7.77(d,J＝8.0Hz,1.28H,minor),7.36(d,J＝8.0Hz,2H,major),7.29-7.27(m,1.28H,minor),7.25-7.23(m,2H,major),7.22-7.20(m,3.20H,minor),7.20-7.19(m,5H,major),7.19-7.18(m,3H,major),7.17-7.15(m,1.92H,minor),7.14-7.13(m,1.28H,minor),7.11(d,J＝4.0Hz,2H,major),7.09-7.07(m,1.28H,minor),7.06-7.04(m,2H,major),6.98(d,J＝7.6Hz,2H,major),6.95(d,J＝8.4Hz,2H,major),6.90(d,J＝7.2Hz,1.28H,minor),6.70(d,J＝8.4Hz,1.28H,minor),6.55(s,1H,major),6.52(d,J＝8.4Hz,2H,major),6.46(d,J＝8.4Hz,1.28H,minor),6.38(s,0.64H,minor),4.53(s,2H,major),4.52-4.50(m,1.28H,minor),4.50-4.48(m,1.28H,minor),4.46(s,2H,major),3.01(s,3H,major),2.96(s,1.92H,minor),2.92-2.89(m,1H,major),2.89-2.86(s,0.64H,minor),2.44(s,1.92H,minor),2.36(s,3H,major),1.26(s,3H,major),1.25(s,1.92H,minor),1.24(s,3H,major),1.23(s,1.92H,minor)ppm；
Compound 2r
Yellow oil (132mg, 77%, PE/EA = 15). E/Z>20:1. 1 H NMR(400MHz,CDCl 3 )δ7.47(d,J＝7.6Hz,2H),7.38-7.31(m,4H),7.29-7.24(m,2H),7.23-7.20(m,2H),7.20-7.13(m,5H),6.98(d,J＝8.4Hz,2H),6.93-6.87(m,2H),6.61-6.53(m,1H),6.22(s,1H),6.13-6.05(m,2H),4.49(s,2H),4.44(s,2H),2.97(s,3H),2.43(s,3H),2.33(s,3H)ppm；
Compound 2s
Yellow oil (81mg, 52%, PE/EA = 15). E/Z = 74. 1 HNMR(400MHz,CDCl 3 )δ7.75(d,J＝8.0Hz,0.6H,minor),7.46(d,J＝7.6Hz,2H,major),7.38-7.34(m,2H,major),7.29-7.28(m,0.6H,minor),7.27-7.26(m,0.6H,minor),7.26-7.23(m,1.2H,minor),7.22-7.18(m,2H,major),7.18-7.14(m,4H,major),7.05-7.03(m,0.6H,minor),7.03-7.01(m,2H,major),6.95-6.91(m,2H,major),6.84-6.76(m,0.6H,minor),6.53-6.51(m,1H,major),6.50-6.49(m,0.3H,minor),6.41-6.34(m,0.3H,minor),6.24(s,0.3H,minor),6.21(s,1H,major),6.10-6.07(m,1H,major),6.04-6.00(m,1H,major),5.87-5.79(m,1H,major),5.79-5.77(m,0.3H,minor),5.18-5.14(m,2H,major),5.13-5.11(m,0.6H,minor),4.45(s,2H,major),3.89-3.86(m,2H,major),3.86-3.85(m,0.6H,minor),2.89(s,3H,major),2.88-2.87(m,0.9H,minor),2.45(s,0.9H,minor),2.44(s,3H,major),2.36(s,3H,major)ppm；
Compound 2t
Yellow oil (147mg, 88%). E/Z = 70. 1 H NMR(400MHz,CDCl 3 )δ7.74-7.70(m,0.72H,minor),7.48-7.45(m,2H,major),7.38-7.35(m,2H,major),7.34-7.31(m,3H,major),7.29-7.27(m,1.08H,minor),7.27-7.26(m,0.72H,minor),7.25-7.22(m,1.08H,minor),7.22-7.19(m,3H,major),7.18-7.16(m,1.44H,minor),7.16-7.12(m,4H,major),7.05-7.02(m,0.72H,minor),6.99-6.96(m,2H,major),6.91-6.88(m,2H,major),6.82-6.78(m,0.72H,minor),6.71(s,1H,major),6.52-6.50(m,0.36H,minor),6.50-6.48(m,1H,major),6.37-6.32(m,0.36H,minor),6.22-6.21(m,0.36H,minor),6.21-6.20(m,1H,major),6.07-6.05(m,1H,major),6.01-5.97(m,1H,major),4.51-4.50(m,0.72H,minor),4.50-4.49(m,2H,major),4.49-4.45(m,0.72H,minor),4.45-4.41(m,2H,major),3.37-3.32(m,2H,major),3.32-3.30(m,0.72H,minor),2.43(s,1.08H,minor),2.41(s,3H,major),2.34(s,3H,major),1.65-1.63(m,0.72H,minor),1.62-1.58(m,2H,major),1.41-1.32(m,4H,major),1.32-1.23(m,1.44H,minor),0.98-0.94(m,3H,major),0.94-0.93(m,1.08H,minor)ppm；
Compound 2u
Yellow oil (113mg, 75%). E/Z = 68. 1 H NMR(400MHz,CDCl 3 )δ7.72(d,J＝8.0Hz,0.8H,minor),7.32(d,J＝8.0Hz,2H,major),7.29-7.27(m,2H,minor),7.18-7.17(m,5H,major),7.17-7.15(m,1.2H,minor),7.13-7.11(m,2H,major),7.11-7.09(m,0.8H,minor),7.09-7.07(m,3H,major),7.02-6.99(m,2H,major),6.89-6.84(m,0.8H,minor),6.76-6.72(m,1H,major),6.71-6.67(m,0.4H,minor),6.58(s,1H,major),6.39(s,0.4H,minor),6.31-6.27(m,1H,major),6.27-6.25(m,0.4H,minor),6.21(dd,J＝8.8,2.4Hz,0.8H,major),6.11-6.05(m,0.4H,minor),4.55(s,0.8H,minor),4.45(s,2H,major),2.93(s,6H,major),2.91(s,2.4H,minor),2.43(s,1.2H,minor),2.37(s,3H,major)ppm；
Compound 2v
White solid (121mg, 72%). E/Z>20:1. 1 H NMR(400MHz,CDCl 3 )δ7.40(d,J＝8.0Hz,2H),7.27-7.25(m,1H),7.24-7.20(m,5H),7.14(d,J＝7.2Hz,2H),7.12-7.07(m,2H),7.02(d,J＝7.2Hz,2H),6.89(d,J＝2.0Hz,1H),6.53(s,1H),6.47(d,J＝8.4Hz,1H),6.31-6.24(m,1H),4.45-4.35(m,2H),2.93(s,6H),2.40(s,3H)ppm；
Compound 2w
Yellow oil (100mg, 65%). E/Z = 87. 1 H NMR(400MHz,CDCl 3 )δ7.59(d,J＝8.4Hz,2H,major),7.38-7.33(m,2H,major),7.31-7.29(m,0.33H,minor),7.28-7.25(m,2H,major),7.24-7.23(m,0.33H,minor),7.23-7.22(m,0.33H,minor),7.21-7.16(m,3H,major),7.16-7.13(m,0.5H,minor),7.12-7.08(m,0.33H,minor),7.07-7.02(m,3H,major),7.03-6.99(m,0.5H,minor),6.90(d,J＝8.8Hz,0.17H,minor),6.86-6.81(m,2H,major),6.71(d,J＝8.8Hz,1H,major),6.51(s,0.17H,minor),6.37(s,1H,major),6.16-6.15(m,0.17H,minor),6.14-6.10(m,1H,major),5.99(d,J＝2.4Hz,0.17H,minor),5.90(d,J＝2.4Hz,1H,major),4.61(s,2H,major),4.51(s,0.33H,minor),3.53(s,0.5H,minor),3.27(s,3H,major),2.95(s,1H,minor),2.94(s,6H,major),2.40(s,3H,major),2.34(s,0.5H,minor)ppm；。
Example 2
Compounds 1b-j,2a-2w were prepared as in example 1.
Synthesis of Compound 1a
Dissolving compound 3 and compound 4in toluene, adding calcium bis (trifluoromethanesulfonimide), reacting for 4 hours under reflux, adding saturated solution of sodium bicarbonate, quenching, and post-treating to obtain compound 1a (67mg, 43%).
Example 3
Compounds 1b-j,2a-2w were prepared as in example 1.
Synthesis of Compound 1a
Compound 3 and compound 4 were dissolved in toluene, silver bis (trifluoromethanesulfonimide) was added, reacted for 4 hours under reflux, quenched with saturated sodium bicarbonate solution, and worked up to give compound 1a (85mg, 56%).

Claims (6)

1. A method for synthesizing para-substituted aniline compounds 1 and 2 with the structure of formula (1) is characterized in that,
Figure FDA0003302571360000011
the following reaction scheme was used:
Figure FDA0003302571360000012
wherein R is 1 Refers to methyl, ethyl, n-butyl, allyl, cyclohexyl, benzyl, 3-methylbenzyl, 3-fluorobenzyl, 3-chlorobenzyl, 3-trifluoromethylbenzyl, 4-tert-butylbenzyl, 4-bromobenzyl, 4-isopropylbenzyl; r is 2 Refers to methyl, ethyl, n-butyl, allyl, cyclopropyl, cyclohexyl, benzyl, 3-methylbenzyl, 3-fluorobenzyl, 3-chlorobenzyl, 3-trifluoromethylbenzyl, 4-tert-butylbenzyl, 4-bromobenzyl, 4-isopropylbenzyl; r 3 Is phenyl, 2-bromophenyl, 2-trifluoromethylphenyl, 2-methoxyphenyl, 4-fluorophenyl, 4-chlorophenyl, 4-bromophenyl, 4-methylphenyl, 4-methoxyphenyl; r 4 Refers to benzyl; r 5 Refers to ester group, p-toluenesulfonyl group, p-methylsulfonyl group, 4-chlorobenzenesulfonyl group;
step 1: dissolving compound 3 and compound 4in an organic solvent such as chloroform, carbon tetrachloride, hexafluoro-2-propanol, toluene, 1, 2-dichloroethane, adding a Lewis acid such as silver bis (trifluoromethanesulfonimide), calcium bis (trifluoromethanesulfonimide), tris (pentafluorophenyl) borane, reacting at room temperature or under reflux for 4-8 hours, adding a saturated solution of sodium bicarbonate, quenching, and post-treating to obtain compound 1 or 2.
2. The method of claim 1, wherein the para-substituted aniline compound has the following structure:
Figure FDA0003302571360000021
3. the method of claim 1, wherein the lewis acid is silver bis (trifluoromethanesulfonimide), calcium bis (trifluoromethanesulfonimide), or tris (pentafluorophenyl) borane.
4. The method of claim 1, wherein said one lewis acid is silver bis (trifluoromethanesulfonimide).
5. The method of claim 1, wherein said one organic solvent is selected from the group consisting of chloroform, carbon tetrachloride, hexafluoro-2-propanol, toluene, and 1, 2-dichloroethane.
6. The process of claim 1 wherein said one organic solvent is chloroform or hexafluoro-2-propanol.
CN202111194690.5A 2021-10-13 2021-10-13 Novel method for synthesizing para-substituted aniline compound Pending CN115960056A (en)

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