CN115611777B - Preparation method of para-cyanation product of arylamine compound - Google Patents
Preparation method of para-cyanation product of arylamine compound Download PDFInfo
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Abstract
The invention discloses a preparation method of an arylamine compound para-cyanation product, which comprises the steps of sequentially adding an arylamine derivative, palladium acetate, (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 1-adamantanecarboxylic acid, zinc acetate, silver carbonate and potassium ferricyanate into a glass reaction tube, and reacting at 60-100 ℃ by taking hexafluoroisopropanol as a solvent to obtain the arylamine para-cyanation product. The invention uses the aniline derivative protected by the isobutoxycarbonyl group as a starting material, and the raw materials are easy to obtain and have various types; the product obtained by the method has various types, and can be directly applied to the synthesis of drug molecules and other further reactions; meanwhile, the synthesis route is safe and feasible, the cost is low, the reaction operation and post-treatment processes are simple, the selectivity is good, the side reaction is less, and the amplification reaction can be carried out.
Description
Technical Field
The invention relates to a preparation method of an arylamine compound para-cyanation product, in particular to a preparation method of isobutoxycarbonyl-protected aniline derivative para-selectively cyanation.
Background
Cyano compounds are an important component of structural motifs in dyes, pharmaceutical molecules, agrochemicals and electronic materials. In addition, aryl nitrile as an important intermediate can be converted into various compounds such as carboxylic acid, benzylamine, amide, ketone and the like through hydrolysis, reduction, cycloaddition, nucleophilic addition and other methods, and has wide application in organic synthesis. In the prior art, a great deal of literature reports the cyanation reaction of C-H bonds, and the construction of C-CN bonds is realized. For example, document (1) Li, J. & Ackermann, L.cobalt-Catalyzed C-H Cyanation of Arenes and Healarenes.Angew.chem.Int.Ed.2015, 54,3635-3638. (2) Jayarajan, R., das, J., bag, S., chordhury, R. & Maiti, D.reverse meta-C-H Functionalization of Arenes across Different Linker Lengths.Angew.chem.Int.Ed.2018,57,7659-7663. (3) Zhao, D., "Xu, P. & Ritter, T.Palladium-Catalyzed La-Stage Direct Arene Cyanation.chem 2019,5,97-107. (4) Chen, h., mondeal, A., wedi, P. & van Gemmeren, M.Dual Ligand-Enabled Nondirected C-H cyanidation of Arens. ACS catalyst.2019, 9,1979-1984 (5) Liu, L. -Y.,. Yeung, K. -S. & Yu, J. -Q.Ligand-protein Non-direct C-H cyanidation of Arens. Chem. Eur. J.2019,25,2199-2202, respectively, discloses Cyanation of a C-H bond:
(1)
(2)
among them, the process (1) has poor selectivity, and the process (2) has a difficult synthesis and high cost, so that it is necessary to propose further solutions to the above problems.
Disclosure of Invention
The invention aims to provide a preparation method of para-cyanation products of arylamine compounds.
The technical scheme of the invention is as follows:
a process for preparing para-cyanated products of arylamine compounds, the process comprising: sequentially adding an arylamine derivative, palladium acetate, (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 1-adamantanecarboxylic acid, zinc acetate, silver carbonate and potassium ferricyanate into a glass reaction tube, putting into a stirrer, taking hexafluoroisopropanol as a solvent, fixing the glass reaction tube in a heating stirrer for stirring, and carrying out column chromatography separation and purification treatment on the product after the reaction is finished to obtain an arylamine compound para-cyanation product.
Further, the arylamine compound is any one of the following two structural formulas:
wherein, the liquid crystal display device comprises a liquid crystal display device,
R 1 、R 2 、R 3 、R 4 is any one or two of hydrogen, alkyl and halogen;
R 5 is alkyl group；
R 6 、R 7 Are all hydrogen;
R 8 is alkyl;
m is 1 or 2.
Further, the R 5 Is any one of branched alkyl and cycloalkyl, R 1 、R 2 、R 3 、R 4 Are all hydrogen.
Further, the molar ratio of the aromatic amine derivative, palladium acetate, (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 1-adamantanecarboxylic acid, zinc acetate, silver carbonate and potassium ferricyanate is 1.0:0.1:0.1:0.2:2.0:1.0:0.2.
further, the concentration of hexafluoroisopropanol was 0.15M.
Further, the rotating speed of the heating stirrer is 500rpm, the heating temperature is 60-100 ℃, and the reaction time is 24-48h.
Further, the reaction process is as follows:
the invention provides a preparation method of an arylamine compound para-cyanation product, which has the beneficial effects that:
1. the method uses the aromatic amine derivative and the cyanation reagent as the starting materials, and the raw materials are easy to obtain and have various types;
2. the product obtained by the method has various types, can be directly applied to the synthesis of related drug molecules, and enriches the development of the cyanation research field;
3. the method has the advantages of simple and feasible operation of reaction conditions, simple post-treatment process, less byproducts and capability of carrying out a large amount of reactions.
Detailed Description
The invention provides a preparation method of an arylamine compound para-cyanation product, which comprises the following steps: sequentially adding an aromatic amine derivative, palladium acetate, (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 1-adamantanecarboxylic acid, zinc acetate, silver carbonate and potassium ferricyanate into a glass reaction tube, putting into a stirrer, taking hexafluoroisopropanol as a solvent, fixing the glass reaction tube in a heating stirrer for stirring, and carrying out column chromatography separation and purification treatment on the product after the reaction is finished to obtain an aromatic amine para-cyanation product.
The reaction process of the technical scheme can be expressed as follows:
in order to make the above objects, features and advantages of the present invention more comprehensible, the following embodiments accompanied with examples are further described. The invention is not limited to the embodiments listed but includes any other known modification within the scope of the claims that follow.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
The present embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected aniline derivative as follows: the reaction formula of the isobutoxycarbonyl-protected aniline is as follows:
the method comprises the steps of adding 0.0193 g (0.1 mmol) of isobutoxycarbonyl-protected aniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol) of 1-adamantanecarboxylic acid, 0.0036 g (0.02 mmol), 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 83%).
1 H NMR(400MHz,CDCl 3 )δ7.58(d,J＝8.9Hz,1H),7.52(d,J＝8.8Hz,1H),6.99(s,1H),3.97(d,J＝6.6Hz,1H),2.003-1.91(m,1H),0.96(d,J＝6.7Hz,3H). 13 C NMR(100MHz,CDCl 3 )δ153.3,142.4,133.4,119.1,118.3,106.1,72.0,28.0,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 12 H 14 N 2 O 2 Na:241.0947；Found:241.0950.
Example 2
The present embodiment shows a cyanation preparation method of isobutoxycarbonyl-protected m-fluoroaniline derivative according to the following steps: the reaction formula of the m-fluoroaniline protected by the isobutoxycarbonyl group is as follows:
adding 0.0211 g (0.1 mmol) of isobutoxycarbonyl-protected m-fluoroaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol) of 1-adamantanecarboxylic acid, 0.0036 g (0.02 mmol), 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 70%).
1 H NMR(400MHz,CDCl 3 )δ7.59(d,J＝1.9Hz,1H),7.50(dd,J＝8.5,7.3Hz,1H),7.22(s,1H),7.13(dd,J＝8.6,1.9Hz,1H),3.97(d,J＝6.6Hz,2H),2.03-1.91(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ164.2(d,J＝256.7Hz),153.0,144.7(d,J＝14.6Hz),133.9(d,J＝1.8Hz),114.4,114.1(d,J＝2.9Hz),105.8(d,J＝25.2Hz),94.8(d,J＝15.9Hz),72.2,28.0,19.1. 19 F NMR(377MHz,CDCl 3 )δ-104.26.HRMS(ESI)m/z:[M+Na] + Calcd for C 12 H 13 FN 2 O 2 Na:259.0853；Found:259.0855.
Example 3
The present embodiment shows a cyanation preparation method of isobutoxycarbonyl-protected meta-chloroaniline derivative according to the following steps: the reaction formula of the m-chloroaniline protected by the isobutoxycarbonyl group is as follows:
adding 0.0227 g (0.1 mmol) of isobutoxycarbonyl-protected m-chloroaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol) of 1-adamantanecarboxylic acid, 0.0036 g (0.02 mmol), 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 72%).
1 H NMR(400MHz,CDCl 3 )δ7.74(d,J＝2.0Hz,1H),7.56(d,J＝8.6Hz,1H),7.35(dd,J＝8.6,2.1Hz,1H),7.12(s,1H),3.97(d,J＝6.6Hz,2H),2.03-1.91(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.0,143.4,138.1,134.7,118.9,116.4,116.4,107.0,72.2,28.0,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 12 H 13 ClN 2 O 2 Na:275.0558；Found:275.0561.
Example 4
The present embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected m-bromoaniline derivative as follows: the reaction formula of the m-chloroaniline protected by the isobutoxycarbonyl group is as follows:
adding 0.0271 g (0.1 mmol) of m-bromoaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 58%).
1 H NMR(400MHz,CDCl 3 )δ7.89(d,J＝2.0Hz,1H),7.55(d,J＝8.6Hz,1H),7.42(dd,J＝8.6,2.1Hz,1H),7.13(s,1H),3.97(d,J＝6.6Hz,2H),2.03-1.91(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(10MHz,CDCl 3 )δ153.0,143.2,135.0,126.3,122.0,117.5,116.9,109.4,77.5,77.2,76.8,72.2,28.0,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 12 H 13 BrN 2 O 2 Na:319.0053；Found:319.0049.
Example 5
The present embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected meta-methylaniline derivative according to the following steps: the reaction formula of the m-methylaniline protected by the isobutoxycarbonyl group is as follows:
adding 0.0207 g (0.1 mmol) of m-methylaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 60 ℃ for 48 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (yellow solid, yield 62%).
1 H NMR(400MHz,CDCl 3 )δ7.50(d,J＝8.5Hz,1H),7.42(s,1H),7.29(dd,J＝8.5,1.8Hz,1H),6.96(s,1H),3.96(d,J＝6.6Hz,2H),2.50(s,3H),2.03-1.91(m,1H),0.95(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.3,143.5,142.2,133.69,119.2,118.4,115.8,106.7,71.9,28.0,20.8,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 13 H 16 N 2 O 2 Na:255.1104；Found:255.1098.
Example 6
The present embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected m-ethylaniline derivative as follows: the reaction formula of the m-ethylaniline protected by the isobutoxycarbonyl group is as follows:
0.0221 g (0.1 mmol) of isobutoxycarbonyl-protected m-ethylaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol) of 1-adamantanecarboxylic acid, 0.0036 g (0.02 mmol) of zinc acetate 0.0360 g (0.2 mmol), 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol are added into a reaction tube and reacted for 48 hours at 60 ℃;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 55%).
1 H NMR(400MHz,CDCl 3 )δ7.53(d,J＝8.4Hz,1H),7.42(s,1H),7.30(dd,J＝8.4,1.8Hz,1H),6.89(s,1H),3.97(d,J＝6.6Hz,2H),2.83(q,J＝7.6Hz,2H),2.03-1.91(m,1H),1.28(t,J＝7.6Hz,3H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.3,149.7,142.3,134.0,117.9,115.9,106.1,100.1,72.0,28.0,28.0,19.1,15.0.HRMS(ESI)m/z:[M+Na] + Calcd for C 14 H 18 N 2 O 2 Na:269.1260；Found:269.1253.
Example 7
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected meta-isopropylaniline derivative as follows: the reaction formula of the m-isopropyl aniline protected by the isobutoxycarbonyl group is as follows:
adding 0.0235 g (0.1 mmol) of isobutoxycarbonyl-protected m-isopropylaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 80 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 45%).
1 H NMR(400MHz,CDCl 3 )δ7.53(d,J＝8.5Hz,1H),7.44(d,J＝2.0Hz,1H),7.33(dd,J＝8.5,2.0Hz,1H),6.90(s,1H),3.97(d,J＝6.6Hz,2H),3.40-3.27(m,1H),2.05-1.93(m,1H),1.29(d,J＝6.9Hz,6H),0.97(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ154.2,153.3,142.5,134.1,118.4,116.0,115.3,105.8,72.0,32.6,28.0,23.2,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 15 H 20 N 2 O 2 Na:283.1417；Found:283.1414.
Example 8
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 2, 5-difluoroaniline derivative as follows: the reaction formula of the 2, 5-difluoroaniline protected by the isobutoxycarbonyl group is as follows:
the method comprises the steps of adding 0.0229 g (0.1 mmol) of isobutoxycarbonyl-protected 2, 5-difluoroaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 55%).
1 H NMR(400MHz,CDCl 3 )δ8.17(dd,J＝10.8,6.5Hz,1H),7.30(dd,J＝10.0,5.6Hz,1H),7.14(s,1H),4.01(d,J＝6.7Hz,2H),2.03-1.91(m,1H),0.98(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ160.5(dd,J＝254.3,2.0Hz),152.5,146.9(dd,J＝242.2,2.7Hz),133.3(t,J＝11.9Hz),118.3(dd,J＝24.5,2.1Hz),113.3(d,J＝2.0Hz),107.4(dd,J＝28.9,1.8Hz),93.8(dd,J＝18.6,9.4Hz),72.7,28.0,19.1. 19 F NMR(377MHz,CDCl 3 )δ-107.96(d,J＝14.1Hz),-135.52.HRMS(ESI)m/z:[M+Na] + Calcd for C 12 H 12 F 2 N 2 O 2 Na:277.0759；Found:277.0755.
Example 9
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 2-methyl-5-fluoroaniline derivative according to the following steps: the reaction formula of the 2-methyl-5-fluoroaniline protected by the isobutoxycarbonyl group is as follows:
the method comprises the steps of adding 0.0225 g (0.1 mmol) of 2-methyl-5-fluoroaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 73%).
1 H NMR(400MHz,CDCl 3 )δ8.05(d,J＝11.7Hz,1H),7.33(d,J＝7.0Hz,1H),6.69(s,1H),3.98(d,J＝6.7Hz,2H),2.23(s,3H),2.05-1.93(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ162.8(d,J＝254.5Hz),152.9,142.4(d,J＝11.5Hz),134.0(d,J＝1.5Hz),121.3(d,J＝3.2Hz),114.5,106.4(d,J＝26.2Hz),94.5(d,J＝15.9Hz),72.4,28.0,19.1,16.9. 19 F NMR(377MHz,CDCl 3 )δ-107.22.HRMS(ESI)m/z:[M+Na] + Calcd for C 13 H 15 FN 2 O 2 Na:273.1010；Found:273.1016.
Example 10
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 2-methyl-5-chloroaniline derivative as follows: the reaction formula of the 2-methyl-5-chloroaniline protected by the isobutoxycarbonyl group is as follows:
into a reaction tube, 0.0241 g (0.1 mmol) of isobutoxycarbonyl-protected 2-methyl-5-chloroaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanide and 0.65mL of hexafluoroisopropanol are added for reaction at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 70%).
1 H NMR(400MHz,CDCl 3 )δ8.29(s,1H),7.40(s,1H),6.65(s,1H),3.99(d,J＝6.7Hz,2H),2.25(s,3H),2.04-1.92(m,1H),0.98(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.0,141.8,141.4,135.9,135.1,124.3,119.6,116.4,106.8,72.4,28.0,19.1,17.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 13 H 15 ClN 2 O 2 Na:289.0714；Found:289.0709.
Example 11
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 2-fluoro-5-chloroaniline derivative as follows: the reaction formula of the 2-fluoro-5-chloroaniline protected by the isobutoxycarbonyl group is as follows:
adding 0.0245 g (0.1 mmol) of isobutoxycarbonyl-protected 2-fluoro-5-chloroaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 50%).
1 H NMR(400MHz,CDCl 3 )δ8.44(d,J＝7.0Hz,1H),7.37(d,J＝10.2Hz,1H),7.07(s,1H),4.01(d,J＝6.7Hz,2H),2.06-1.94(m,1H),0.98(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ152.5,149.2(d,J＝245.7Hz),134.1(d,J＝3.4Hz),132.4(d,J＝10.8Hz),120.3(d,J＝1.6Hz),119.5(d,J＝23.6Hz),115.3(d,J＝2.1Hz),106.3(d,J＝9.0Hz),72.7,28.0,19.1. 19 F NMR(377MHz,CDCl 3 )δ-132.55.HRMS(ESI)m/z:[M+Na] + Calcd for C 12 H 12 FClN 2 O 2 Na:293.0464；Found:293.0470.
Example 12
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 2, 5-dimethylaniline derivative according to the following steps: the reaction formula of the 2, 5-dimethylaniline protected by the isobutoxycarbonyl group is as follows:
0.0221 g (0.1 mmol) of isobutoxycarbonyl-protected 2, 5-dimethylaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol are added into a reaction tube and reacted for 24 hours at 100 ℃;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 85%).
1 H NMR(400MHz,CDCl 3 )δ7.99(s,1H),7.34(s,1H),6.59(s,1H),3.97(d,J＝6.7Hz,2H),2.48(s,3H),2.22(s,3H),2.04-1.92(m,1H),0.97(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.3,141.5,140.3,134.1,123.6,120.4,118.5,106.8,72.0,28.0,20.5,19.2,17.0.HRMS(ESI)m/z:[M+Na] + Calcd for C 14 H 18 N 2 O 2 Na:269.1260；Found:269.1265.
Example 13
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 2-methyl-3-fluoroaniline derivative according to the following steps: the reaction formula of the 2-methyl-3-fluoroaniline protected by the isobutoxycarbonyl group is as follows:
the method comprises the steps of adding 0.0225 g (0.1 mmol) of 2-methyl-3-fluoroaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 60%).
1 H NMR(400MHz,CDCl 3 )δ7.97(d,J＝8.7Hz,1H),7.48-7.40(m,1H),6.68(s,1H),3.99(d,J＝6.7Hz,2H),2.20(d,J＝1.8Hz,3H),2.06-1.94(m,1H),0.98(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ161.5(d,J＝253.6Hz),153.1,142.6(d,J＝6.7Hz),131.4(d,J＝1.8Hz),115.1(d,J＝3.2Hz),114.6,113.9(d,J＝17.7Hz),95.3(d,J＝17.2Hz),72.3,28.0,19.1,8.9(d,J＝6.0Hz). 19 F NMR(377MHz,CDCl 3 )δ-108.59.HRMS(ESI)m/z:[M+Na] + Calcd for C 13 H 15 FN 2 O 2 Na:273.1010；Found:273.1017.
Example 14
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 2, 3-dihydro-1H-inden-4-amine derivative as follows: the reaction formula of the isobutoxycarbonyl-protected 2, 3-dihydro-1H-indene-4-amine is as follows:
0.0233 g (0.1 mmol) of isobutoxycarbonyl-protected 2, 3-dihydro-1H-indene-4-amine, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol are added into a reaction tube and reacted at 80 ℃ for 36 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 78%).
1 H NMR(400MHz,CDCl 3 )δ7.91(d,J＝8.4Hz,1H),7.41(d,J＝8.5Hz,1H),6.63(s,1H),3.96(d,J＝6.7Hz,2H),3.10(t,J＝7.6Hz,2H),2.85(t,J＝7.4Hz,2H),2.24-2.14(m,2H),2.04-1.92(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.2,149.5,138.6,132.3,131.8,118.4,116.5,102.7,72.0,33.1,30.0,28.0,24.2,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 15 H 18 N 2 O 2 Na:281.1260；Found:281.1265.
Example 15
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 1-aminotetralin derivative as follows: the reaction formula of the 1-aminotetralin protected by the isobutoxycarbonyl group is as follows:
the method comprises the steps of adding 0.0247 g (0.1 mmol) of isobutoxycarbonyl-protected 1-aminotetralin, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 80 ℃ for 36 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (yellow solid, yield 70%).
1 H NMR(400MHz,CDCl 3 )δ7.95(d,J＝8.5Hz,1H),7.47(d,J＝8.6Hz,1H),6.60(s,1H),3.97(d,J＝6.7Hz,2H),2.95(t,J＝6.1Hz,2H),2.55(t,J＝6.2Hz,2H),2.04-1.92(m,1H),1.91-1.78(m,4H),0.97(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.4,141.7,140.1,131.2,126.0,118.4,116.9,107.1,71.9,28.7,28.0,24.2,22.2,21.7,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 16 H 20 N 2 O 2 Na:295.1417；Found:295.1417.
Example 16
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 3-methyl-5-fluoroaniline derivative according to the following steps: the 3-methyl-5-fluoroaniline protected by the isobutoxycarbonyl group is used as a raw material, and the reaction formula is as follows:
the method comprises the steps of adding 0.0225 g (0.1 mmol) of 3-methyl-5-fluoroaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (yellow solid, yield 63%).
1 H NMR(400MHz,CDCl 3 )δ7.34(dd,J＝11.0,1.6Hz,1H),7.02(s,1H),6.96(s,1H),3.97(d,J＝6.6Hz,2H),2.49(s,3H),2.03-1.91(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ164.5(d,J＝255.8Hz),153.0,144.8,143.6(d,J＝12.3Hz),114.7,113.7,103.2(d,J＝25.4Hz),96.0(d,J＝15.5Hz),72.2,28.0,20.7,19.1. 19 F NMR(377MHz,CDCl 3 )δ-111.60.HRMS(ESI)m/z:[M+Na] + Calcd for C 13 H 15 FN 2 O 2 Na:273.1010；Found:273.1002.
Example 17
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl protected 3-methyl-5-chloroaniline derivative according to the following steps: the 3-methyl-5-chloroaniline protected by the isobutoxycarbonyl group is used as a raw material, and the reaction formula is as follows:
/>
into a reaction tube, 0.0241 g (0.1 mmol) of 3-methyl-5-chloroaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanide and 0.65mL of hexafluoroisopropanol are added for reaction at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (yellow solid, yield 53%).
1 H NMR(400MHz,CDCl 3 )δ7.51(d,J＝1.6Hz,1H),7.24(s,1H),7.03(s,1H),3.97(d,J＝6.6Hz,2H),2.03-1.91(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.0,145.3,142.6,138.1,117.3,116.4,115.6,107.7,72.2,28.0,21.3,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 13 H 15 ClN 2 O 2 Na:289.0714；Found:289.0715.
Example 18
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 3, 5-difluoroaniline derivative as follows: the 3, 5-difluoroaniline protected by the isobutoxycarbonyl group is used as a raw material, and the reaction formula is as follows:
the method comprises the steps of adding 0.0229 g (0.1 mmol) of 3, 5-difluoroaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol), 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (pale yellow solid, yield 50%).
1 H NMR(400MHz,CDCl 3 )δ7.19(d,J＝9.4Hz,2H),7.09(s,1H),3.99(d,J＝6.6Hz,2H),2.04-1.92(m,1H),0.97(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ164.0(dd,J＝257.9,6.9Hz),152.7,145.1(t,J＝13.6Hz),109.6,101.6(dd,J＝25.1,3.1Hz),86.1(t,J＝19.6Hz),72.5,28.0,19.1. 19 F NMR(377MHz,CDCl 3 )δ-102.81.HRMS(ESI)m/z:[M+Na] + Calcd for C 12 H 12 F 2 N 2 O 2 Na:277.0759；Found:277.0761.
Example 19
This embodiment shows a cyanation preparation method of an isobutoxycarbonyl-protected 3, 5-dimethylaniline derivative according to the following steps: the 3, 5-dimethylaniline protected by the isobutoxycarbonyl group is used as a raw material, and the reaction formula is as follows:
0.0221 g (0.1 mmol) of 3, 5-dimethylaniline protected by isobutoxycarbonyl, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0036 g (0.02 mmol) of 1-adamantanecarboxylic acid, 0.0360 g (0.2 mmol) of zinc acetate, 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol are added into a reaction tube and reacted for 24 hours at 100 ℃;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 80%).
1 H NMR(400MHz,CDCl 3 )δ7.19(s,2H),6.80(s,1H),3.95(d,J＝6.6Hz,2H),2.48(s,6H),2.03-1.91(m,1H),0.96(d,J＝6.7Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ153.3,143.7,141.6,117.6,116.7,107.6,71.9,28.0,21.0,19.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 14 H 18 N 2 O 2 Na:269.1260；Found:269.1668.
Example 20
The present embodiment shows a cyanation preparation method of an isopropyloxycarbonyl-protected aniline derivative as follows: the reaction formula of the aniline protected by isopropyl oxycarbonyl is as follows:
adding 0.0179 g (0.1 mmol) of isopropyloxycarbonyl-protected aniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol) of 1-adamantanecarboxylic acid, 0.0036 g (0.02 mmol) of zinc acetate 0.0360 g (0.2 mmol), 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol into a reaction tube, and reacting at 100 ℃ for 24 hours;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the target product (white solid, yield 75%).
1 H NMR(400MHz,CDCl 3 )δ7.57(d,J＝8.9Hz,2H),7.51(d,J＝8.9Hz,2H),7.00(s,1H),5.07-4.96(m,1H),1.29(d,J＝6.3Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ152.7,142.5,133.4,119.1,118.3,106.0,69.70,22.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 11 H 12 N 2 O 2 Na:227.0791；Found:227.0795.
Example 21
The present embodiment shows a cyanation preparation method of an isopropyloxycarbonyl-protected o-chloroaniline derivative according to the following steps: the reaction formula of the o-chloroaniline protected by isopropyl oxycarbonyl is as follows:
0.0213 g (0.1 mmol) of isopropyl oxycarbonyl-protected o-chloroaniline, 0.0022 g (0.01 mmol) of palladium acetate, 0.0023 g (0.01 mmol) of (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 0.0023 g (0.01 mmol) of 1-adamantanecarboxylic acid, 0.0036 g (0.02 mmol) of zinc acetate 0.0360 g (0.2 mmol), 0.0275 g (0.1 mmol) of silver carbonate, 0.0065 g (0.02 mmol) of potassium ferricyanate and 0.65mL of hexafluoroisopropanol are added into a reaction tube, and the mixture is reacted for 24 hours at 100 ℃;
the TLC tracking reaction is carried out until the reaction is completely finished;
the crude product obtained after the reaction was completed was separated by column chromatography (petroleum ether: ethyl acetate=20:1) to give the objective product (white solid, yield 63%).
1 H NMR(400MHz,CDCl 3 )δ7.74(d,J＝2.0Hz,1H),7.55(d,J＝8.6Hz,1H),7.32(dd,J＝8.6,2.1Hz,1H),7.04(s,1H),5.07-4.96(m,1H),1.30(d,J＝6.3Hz,6H). 13 C NMR(100MHz,CDCl 3 )δ152.5,143.5,138.0,134.7,118.9,116.4,106.8,70.2,22.1.HRMS(ESI)m/z:[M+Na] + Calcd for C 11 H 11 ClN 2 O 2 Na:261.0401；Found:261.0497..
Compared with the prior art, the invention has the beneficial effects that: the preparation method of the para-cyanation product of the arylamine compound adopts palladium acetate as a catalyst to realize high para-selective cyano functionalization of the arylamine derivative, and the synthesis method is simple, convenient, safe and easy to operate; the raw materials are widely and easily available, the cost is low, the construction of the aromatic amine derivative substituted by cyano functional groups is greatly promoted, the related medicine molecules are widely developed, and the application range of the aromatic amine derivative in the fields of medicine, pharmacy, life science and the like is expanded.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (1)
1. The preparation method of the para-cyanation product of the arylamine compound is characterized by comprising the following steps: sequentially adding an aromatic amine derivative, palladium acetate, (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 1-adamantanecarboxylic acid, zinc acetate, silver carbonate and potassium ferricyanate into a glass reaction tube, putting into a stirrer, taking hexafluoroisopropanol as a solvent, fixing the glass reaction tube in a heating stirrer for stirring, carrying out column chromatography separation and purification treatment on the product after the reaction is finished to obtain an aromatic amine compound para-cyanation product,
wherein, the molar ratio of the aromatic amine derivative, palladium acetate, (1R, 4S) -1,11,11-trimethyl-1, 2,3, 4-tetrahydro-1, 4-methylphenazine, 1-adamantanecarboxylic acid, zinc acetate, silver carbonate and potassium ferricyanate is 1.0:0.1:0.1:0.2:2.0:1.0:0.2, the concentration of hexafluoroisopropanol is 0.15M, the rotating speed of the heating stirrer is 500rpm, the heating temperature is 60-100 ℃, the reaction time is 24-48h,
the structural general formula of the arylamine compound is as follows:
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Non-Patent Citations (3)
| Title |
|---|
| "Cu(I) Camphor Coordination Polymers: Synthesis and Study of the Catalytic Activity for Cyclization of 4-Pentyn-1-oic Acid";Tiago A. Fernandes et al.;JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY;第52卷;第3316–3323页 * |
| "Dual Ligand-Enabled Nondirected C−H Cyanation of Arenes";Hao Chen et al.;ACS Catal.;第9卷;第1979-1984页 * |
| "Ligand-Promoted Non-Directed C-H Cyanation of Arenes";Luo-Yan Liu et al.;Chem. Eur. J.;第25卷;第2199-2202页 * |
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