CN112094288B - Selective catalytic synthesis of aryl silicon amide compounds by ferric salt/isopropyl magnesium chloride and preparation method thereof - Google Patents
Selective catalytic synthesis of aryl silicon amide compounds by ferric salt/isopropyl magnesium chloride and preparation method thereof Download PDFInfo
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- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
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Abstract
The invention relates to an aromatic silicon amide compound selectively synthesized by ferric salt/isopropyl magnesium chloride through catalysis and a preparation method thereof. The invention realizes the high-selectivity silicon-based activation of the para-carbon-hydrogen bond of the aryl amide at room temperature based on the synergistic catalysis of the iron salt and the isopropyl magnesium chloride, has the advantages of low cost, mild reaction condition, high selectivity and the like, and avoids the use of a noble metal catalyst under the harsh condition of high temperature and higher cost. The invention is suitable for para-position high-selectivity silicon alkylation of benzamide derivatives with different nitrogen substituents and aryl substituents.
Description
Technical Field
The invention belongs to the technical field of aryl silicon compounds, and relates to an aryl silicon amide compound synthesized by selectively catalyzing ferric salt/isopropyl magnesium chloride and a preparation method thereof.
Background
Aryl silicon compounds are important synthetic intermediates and widely applied to the fields of pharmaceutical chemistry, material chemistry, organic synthetic chemistry and the like. For example: the introduction of silicon-based groups in drug molecules can effectively improve the stability, solubility and drug metabolism speed of the drug, and silicon has special advantages in the aspects of improving drug effect and selectivity and reducing toxicity when replacing the drug molecules; in the field of materials science, aryl silicon compounds are also synthetic monomers of many high molecular polymers; meanwhile, in organic synthesis, a series of transformations can be carried out on carbon-silicon bonds, so that new carbon-carbon bonds and carbon-miscellaneous bonds can be constructed. Currently, the high selectivity silicification reaction of aniline para-position can be realized by utilizing metal iron and copper. At present, the method for realizing the para-position high-selectivity silicification reaction by using benzamide derivatives as substrates has not been reported.
Disclosure of Invention
Technical problem to be solved
In order to avoid the defects of the prior art, the invention provides an aryl silicon amide compound selectively synthesized by ferric salt/isopropyl magnesium chloride through catalysis and a preparation method thereof. Taking iron salt and isopropyl magnesium chloride as catalysts and tetrahydrofuran as a solvent, stirring and reacting the benzamide derivative and chlorosilane at normal temperature, and separating and purifying a product after the reaction to obtain a silicon-based product.
Technical scheme
A method for selectively catalyzing and synthesizing aryl silicon amide compounds by ferric salt/isopropyl magnesium chloride is characterized in that:
when the arylamide is a compound of formula I, the silicatization product is a compound of formula I';
formula I and I', R 1 Is 2-methoxy, 2-ethoxy, 2-hydroxy, 3-fluoro, 3-methoxy, 3-phenoxy, 3-methyl, 3-methylthio, 3-phenyl, 3-oxytrifluoromethyl, 3-methoxy, 3-fluoro-5-methoxy, 3, 5-dimethyl, 3, 5-difluoro, 2-methoxy-5-fluoro, 2, 5-dimethoxy;
when the aryl amide is a compound of formula II, the silicon-based product is a compound of formula II';
when the arylamide is a compound of formula III, the silylation product is a compound of formula III';
when the aryl amide is the compound shown in the formula IV, the silicon-based product is the compound shown in the formula IV';
when the arylamide is a compound of formula v, the siliconized product is a compound of formula v';
when the aryl amide is a compound of formula VI, the silicon alkylation product is a compound of formula VI';
VI and VI', R 2 Is methyl, ethyl, isopropyl;
when the aryl amide is a compound of formula VII, the silicon-based product is a compound of formula VII';
VII and VII', R 3 Is dimethylphenyl, dimethylbutyl, dimethyl-3, 3, 3-fluoropropyl; dimethyl octadecyl radical.
A preparation method for synthesizing aryl silicon compounds by catalyzing aryl amide and chlorosilane with iron is characterized by comprising the following steps:
step 1: stirring benzamide, ferric salt, isopropyl magnesium chloride and 3-5 times of solvent at room temperature for 30-40 min, adding chlorosilane, reacting at normal temperature for 24-48 h, and performing TLC tracking reaction;
the molar ratio of the benzamide to the ferric salt to the isopropyl magnesium chloride to the chlorosilane is 1:0.1:4: 3-1: 0.2:5:4
Step 2: after the reaction was completed, the reaction mixture was poured into an aqueous ammonium chloride solution and extracted with ethyl acetate;
and 3, step 3: then using anhydrous Na 2 SO 4 Drying, and separating by column chromatography with petroleum ether/ethyl acetate 20:1 as developing agent to obtain aryl silicon compounds.
The Fe catalysts include, but are not limited to: ferric chloride, ferrous chloride, ferric triflate or ferric acetylacetonate.
Such solvents include, but are not limited to: tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, toluene, n-hexane, 1, 4-dioxane, 1, 2-dichloroethane or nitromethane.
Advantageous effects
The invention provides a method for selectively catalyzing and synthesizing aryl silicon amide compounds by ferric salt/isopropyl magnesium chloride and a preparation method thereof. The invention realizes the high-selectivity silicon-based activation of the para-carbon-hydrogen bond of the aryl amide at room temperature based on the synergistic catalysis of the iron salt and the isopropyl magnesium chloride, has the advantages of low cost, mild reaction condition, high selectivity and the like, and avoids the use of a noble metal catalyst under the harsh condition of high temperature and higher cost. The invention is suitable for para-position high-selectivity silicon alkylation of benzamide derivatives with different nitrogen substituents and aryl substituents.
The invention takes metallic iron as a catalyst for the first time, and realizes the room-temperature aryl amide para-position high-selectivity silicification reaction under the synergistic action of isopropyl magnesium chloride and chlorosilane, so as to obtain the corresponding aryl silicon amide compound. The method has the advantages of low cost, mild reaction conditions, high selectivity and the like, and avoids the use of a noble metal catalyst under severe high-temperature conditions and with higher cost. The method is suitable for para-position high-selectivity silicon alkylation of benzamide derivatives substituted by different nitrogen substituents and aryl groups.
Detailed Description
The invention will now be further described with reference to the examples:
example 1
4-trimethylsilyl-N-tert-butylbenzamide
Under an argon atmosphere, N-tert-butylbenzamide (0.2mmol), (0.02mmol) was chlorinatedFerrous iron is added to 0.5ml tetrahydrofuran, 0.4ml tetrahydrofuran solution of 2mol/L isopropyl magnesium chloride is slowly added dropwise at normal temperature, stirred for 30 minutes, then 0.6mmol trimethylchlorosilane is added, the reaction is stirred at normal temperature for 48 hours, 5ml saturated aqueous ammonium chloride solution is added to quench the reaction, ethyl acetate (10 ml each, 3 times) is used, the extracts are combined, anhydrous sodium sulfate is added and dried, and the mixture is treated with petroleum ether: the product was isolated by column chromatography using ethyl acetate 20:1 as developing solvent to give 4-trimethylsilyl-N-tert-butylbenzamide in 74% yield. The resulting product bopp data and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝7.68(d,J＝8.1Hz,2H),7.55(d,J＝8.1Hz,2H),5.96(brs,1H),1.46(s,9H),0.27(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ＝167.0,144.4,136.1,133.5,125.8,51.6,28.9,-1.3.HRMS(ESI + ):calcd for C 14 H 24 NOSi[M+H] + 250.16272,found 250.16160.
example 2
2-methoxy-4-trimethylsilyl-N-tert-butylbenzamide
Under argon atmosphere, adding (0.2mmol) 2-methoxy-N-tert-butylbenzoamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly adding dropwise a solution of 0.4ml 2mol/L isopropyl magnesium chloride in tetrahydrofuran at room temperature, stirring for 40 minutes, then adding 0.6mmol trimethylchlorosilane, stirring at room temperature for reaction for 30 hours, adding 5ml saturated aqueous ammonium chloride solution to quench the reaction, adding ethyl acetate (10 ml each, 3 times), combining the extracts, adding anhydrous sodium sulfate, drying with petroleum ether: the product was isolated by column chromatography using ethyl acetate 30:1 as developing solvent to give the silica-based product in 56% yield. The resulting product bopp data and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝8.13(d,J＝7.6Hz,1H),7.86(brs,1H),7.21(dd,J＝7.6,0.8Hz,1H),7.05(s,1H),3.97(s,3H),1.45(s,9H),0.27(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ＝164.2,156.4,146.2,131.0,126.3,123.0,115.6,55.8,50.9,28.9,-1.3.HRMS(ESI + ):calcd for C 15 H 26 NO 2 Si[M+H] + 280.17328,found 280.17197.
example 3
3, 5-dimethoxy-4-trimethylsilyl-N-tert-butylbenzamide
Under argon atmosphere, adding (0.2mmol)3, 5-dimethoxy-N-tert-butylbenzoyl formamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly adding dropwise a 2mol/L tetrahydrofuran solution of isopropyl magnesium chloride 0.4ml at normal temperature, stirring for 40 minutes, then adding trimethylchlorosilane 0.6mmol, stirring at normal temperature for reaction for 48 hours, adding saturated aqueous ammonium chloride 5ml to quench the reaction, adding ethyl acetate (10 ml each time, 3 times), combining the extracts, adding anhydrous sodium sulfate, and drying with petroleum ether: the product was isolated by column chromatography using ethyl acetate 30:1 as developing solvent to give the silica-based product in 74% yield. The resulting product bopp and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝6.80(s,2H),6.05(brs,1H),3.76(s,6H),1.45(s,9H),0.26(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ＝167.0,165.2,139.1,117.7,101.8,55.23,51.5,28.7,1.1.HRMS(ESI + ):calcd for C 16 H 28 NO 3 Si[M+H] + 310.18385,found 310.18236.
example 4
3-fluoro-4-trimethylsilyl-5-methoxy-N-tert-butylbenzamide
Under the argon atmosphere, adding (0.2mmol) 3-fluoro-5-methoxy-N-tert-butylbenzamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly dropwise adding 0.4ml tetrahydrofuran solution of 2mol/L isopropyl magnesium chloride at normal temperature, stirring for 30 minutes, and then adding 0.6mmol trimethylchlorosilaneAfter the reaction was stirred at room temperature for 24 hours, 5ml of a saturated aqueous ammonium chloride solution was added to quench the reaction, and ethyl acetate (10 ml each, 3 times) was added to the reaction solution, and the extracts were combined, dried over anhydrous sodium sulfate, and separated with petroleum ether: the product was isolated by column chromatography using ethyl acetate 40:1 as developing solvent to give the silica-based product in 74% yield. The resulting product bopp and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝7.05(d,J＝0.9Hz,1H),6.79(dd,J＝9.0,1.1Hz,1H),5.99(brs,1H),3.80(s,3H),1.44(s,9H),0.29(d,J＝1.9Hz,9H)； 13 C NMR(100MHz,CDCl 3 )δ＝167.0(d,J＝243.0Hz),165.8(d,J＝5.0Hz),165.5(d,J＝16.0Hz),139.5(d,J＝9.0Hz),117.0(d,J＝32Hz),105.7(d,J＝30.0Hz),104.6(d,J＝2.0Hz),55.5,51.7,28.7,0.3(d,J＝16.0Hz)； 19 F NMR(470MHz,CDCl 3 )δ＝-98.0.HRMS(ESI + ):calcd for C 15 H 25 NO 2 FSi[M+H] + 298.16386,found298.16243.
example 5
3, 5-methyl-N-tert-butylbenzamide
Under argon atmosphere, adding (0.2mmol)3, 5-methyl-N-tert-butylbenzoyl formamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly adding dropwise a solution of 0.4ml 2mol/L isopropyl magnesium chloride in tetrahydrofuran at room temperature, stirring for 30 minutes, then adding 0.6mmol trimethylchlorosilane, stirring at room temperature for reaction for 48 hours, adding 5ml saturated aqueous ammonium chloride solution to quench the reaction, using ethyl acetate (10 ml each, 3 times), combining the extracts, adding anhydrous sodium sulfate, drying with petroleum ether: the product was isolated by column chromatography using ethyl acetate 20:1 as developing solvent to give the silica-based product in 48% yield. The resulting product bopp data and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝7.50(s,2H),2.51(s,6H),1.20(d,J＝6.8Hz,9H),0.42(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ166.2,144.6,143.2,136.0,127.3,35.23,24.9,19.2,3.2.HRMS(ESI + ):calcd for C 16 H 28 NOSi[M+H] + 278.19402,found 278.19392.
example 6
2, 5-dimethoxy-4-trimethylsilyl-N-tert-butylbenzamide
Under argon atmosphere, adding (0.2mmol)2, 5-dimethoxy-N-tert-butylbenzoyl amide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly adding dropwise a solution of 0.4ml 2mol/L isopropyl magnesium chloride in tetrahydrofuran at room temperature, stirring for 30 minutes, then adding 0.6mmol trimethylchlorosilane, stirring at room temperature for reaction for 48 hours, adding 5ml saturated aqueous ammonium chloride solution to quench the reaction, using ethyl acetate (10 ml each, 3 times), combining the extracts, adding anhydrous sodium sulfate, drying with petroleum ether: the product was isolated by column chromatography using ethyl acetate 20:1 as developing solvent to give the silica-based product in 74% yield. The resulting product bopp and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝8.05(brs,1H),7.66(s,1H),6.95(s,1H),3.91(s,3H),3.81(s,3H),1.45(s,9H),0.27(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ＝164.2,158.8,151.1,133.3,124.1,118.7,111.9,56.7,55.7,51.0,28.9,-1.1.HRMS(ESI + ):calcd for C 16 H 28 NO 3 Si[M+H] + 310.18385,found 310.18221.
example 7
1-naphthalene-4-trimethylsilyl-N-tert-butylbenzamide
Under the atmosphere of argon, adding (0.2mmol) 1-naphthalene-N-tert-butylbenzoyl formamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly dropwise adding 0.4ml 2mol/L tetrahydrofuran solution of isopropyl magnesium chloride at normal temperature, stirring for 30 min, then adding 0.6mmol trimethylchlorosilane, stirring at normal temperature for reaction for 48h, adding 5ml saturated ammonium chloride aqueous solutionThe reaction was quenched with ethyl acetate (10 ml each, 3 times), the extracts combined and dried over anhydrous sodium sulfate, with petroleum ether: the product was isolated by column chromatography using ethyl acetate 40:1 as developing solvent to give the silica-based product in 80% yield. The resulting product bopp data and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝8.31–8.24(m,1H),8.15–8.09(m,1H),7.65(d,J＝6.9Hz,1H),7.58–7.51(m,2H),7.48(d,J＝6.9Hz,1H),5.81(brs,1H),1.53(s,9H),0.47(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ169.3,140.9,137.3,137.0,132.1,129.7,128.4,126.3,126.2,126.0,123.2,52.0,28.9,0.1.HRMS(ESI + ):calcd for C 18 H 26 NOSi[M+H] + 300.17837,found 300.17688.
example 8
5-trimethylsilyl-2-N-tert-butylfurancarboxamide
Under argon atmosphere, adding (0.2mmol) 2-N-tert-butyl furan formamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly adding 0.4ml 2mol/L tetrahydrofuran solution of isopropyl magnesium chloride dropwise at normal temperature, stirring for 30 minutes, then adding 0.6mmol trimethylchlorosilane, stirring at normal temperature for reaction for 48 hours, adding 5ml saturated aqueous ammonium chloride solution to quench the reaction, adding ethyl acetate (10 ml each time, 3 times), combining the extracts, adding anhydrous sodium sulfate, and drying with petroleum ether: the product was isolated by column chromatography using ethyl acetate 50:1 as developing solvent to give the silica-based product in 60% yield. The resulting product bopp and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝7.37(d,J＝1.6Hz,1H),6.44(d,J＝1.6Hz,1H),6.24(brs,1H),1.44(s,9H),0.30(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ＝158.2,152.1,141.9,123.9,117.0,51.1,28.9,-1.0.HRMS(ESI + ):calcd for C 12 H 21 NO 2 NaSi[M+Na] + 262.12393,found 262.12292.
example 9
5-trimethylsilyl-3-N-tert-butylthiophenecarboxamide
Under argon atmosphere, adding (0.2mmol) 3-N-tert-butylthiophenecarboxamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly dropwise adding 0.4ml tetrahydrofuran solution of 2mol/L isopropyl magnesium chloride at normal temperature, stirring for 30 minutes, then adding 0.6mmol trimethylchlorosilane, stirring at normal temperature for reaction for 28 hours, adding 5ml saturated aqueous ammonium chloride solution to quench the reaction, using ethyl acetate (10 ml each, 3 times), combining the extracts, adding anhydrous sodium sulfate, drying with petroleum ether: the product was isolated by column chromatography using ethyl acetate 50:1 as developing solvent to give the silica-based product in 75% yield. The resulting product bopp data and mass spectral data were: 1 H NMR(400MHz,CDCl 3 )δ＝7.48(d,J＝4.8Hz,1H),7.24(d,J＝4.8Hz,1H),5.68(brs,1H),1.45(s,9H),0.39(s,9H)； 13 C NMR(100MHz,CDCl 3 )δ＝164.7,144.9,144.2,130.1,127.3,51.5,28.8,0.0.HRMS(ESI + ):calcd for C 12 H 21 NOSNaSi[M+Na] + 278.10108,found 278.10008.
example 10
4-trimethylsilyl-N-methylbenzamide
Under argon atmosphere, adding (0.2mmol) N-methylbenzamide, (0.02mmol) ferrous chloride into 0.5ml tetrahydrofuran, slowly dropwise adding 0.4ml of 2mol/L tetrahydrofuran solution of isopropyl magnesium chloride at normal temperature, stirring for 30 minutes, then adding 0.6mmol trimethylchlorosilane, stirring at normal temperature for reaction for 48 hours, adding 5ml of saturated aqueous ammonium chloride solution for quenching reaction, using ethyl acetate (10 ml each time, 3 times), combining extracts, adding anhydrous sodium sulfate, and drying with petroleum ether: the product was isolated by column chromatography using ethyl acetate 30:1 as developing solvent to give the silica-based product in 40% yield. The obtained productThe data of the object wave spectrum and the mass spectrum are as follows: 1 H NMR(400MHz,CDCl 3 )δ＝7.73(d,J＝8.0Hz,2H),7.57(d,J＝8.1Hz,2H),6.28(brs,1H),3.01(d,J＝4.2Hz,3H),0.28(s,9H)； 13 C NMR(100 MHz,CDCl 3 )δ168.4,144.8,134.6,133.5,125.9,26.8,-1.3.HRMS(ESI + ):calcd for C 11 H 18 NOSi[M+H] + 208.11577,found 208.11480。
Claims (2)
1. a method for catalytically synthesizing aryl silicon amide compounds is characterized by comprising the following steps: ferrous chloride and isopropyl magnesium chloride are used as reaction catalysts, and the method comprises the following steps:
step 1: stirring arylamide, ferrous chloride, isopropyl magnesium chloride and 3-5 times of solvent at room temperature for 30-40 min, adding chlorosilane, reacting at room temperature for 24-48 h, and performing TLC tracking reaction;
the molar ratio of the aryl amide to the ferrous chloride to the isopropyl magnesium chloride to the chlorosilane is 1:0.1:4: 3-1: 0.2:5:4
Step 2: after the reaction was completed, the reaction mixture was poured into an aqueous ammonium chloride solution and extracted with ethyl acetate;
and step 3: then using anhydrous Na 2 SO 4 Drying, and separating the product by column chromatography with petroleum ether/ethyl acetate 20:1 as developing agent to obtain aryl silicon compounds, wherein the aryl amide compounds are compounds of formula I-formula VII:
when the arylamide is a compound of formula I, the siliconized product is a compound of formula I';
formula I and I', R 1 Is 2-methoxy, 2-ethoxy, 2-hydroxy, 3-fluoro, 3-phenoxy, 3-methyl, 3-methylthio, 3-phenyl, 3-oxytrifluoromethyl, 3-methoxy, 3-fluoro-5-methoxy, 3, 5-dimethyl, 3, 5-difluoro, 2-methoxy-5-fluoro, 2, 5-dimethoxy;
when the aryl amide is a compound of formula II, the silicon-based product is a compound of formula II';
when the arylamide is a compound of formula III, the siliconized product is a compound of formula III';
when the aryl amide is the compound shown in the formula IV, the silicon-based product is the compound shown in the formula IV';
when the aryl amide is a compound of formula V, the silylation product is a compound of formula V';
when the aryl amide is a compound of formula VI, the silicon alkylation product is a compound of formula VI';
VI and VI', R 2 Is methyl, ethyl, isopropyl;
when the aryl amide is a compound of formula VII, the silicon-based alkylation product is a compound of formula VII';
VII and VII', R 3 Is dimethylphenyl, dimethylbutyl, dimethyl-3, 3, 3-fluoropropyl; dimethyl octadecyl radical.
2. The method of claim 1, the solvent being: tetrahydrofuran, 2-methyltetrahydrofuran, diethyl ether, toluene, n-hexane, 1, 4-dioxane, 1, 2-dichloroethane or nitromethane.
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Non-Patent Citations (4)
| Title |
|---|
| A Convenient Iron-Catalyzed Method for the Preparation of 1,2-Bis(trimethylsilyl)benzenes;Samuel L. Bader 等;《SYNTHESIS》;20100701(第16期);第2759–2762页 * |
| An Electroreductive Approach to Radical Silylation via the Activation of Strong Si−Cl Bond;Lingxiang Lu 等;《J.Am.Chem.Soc.》;20201208;第142卷;第21272-21278页 * |
| Chromium-catalyzed para-selective formation of quaternary carbon centers by alkylation of benzamide derivatives;Pei Liu 等;《NATURE COMMUNICATIONS》;20181106;第9卷(第1期);第1-8页 * |
| Silver-catalyzed transmetalation between chlorosilanes and aryl and alkenyl Grignard reagents for the synthesis of tetraorganosilanes;Murakami, Kei 等;《Angewandte Chemie》;20081231;第47卷(第31期);第5833-5835页 * |
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