Method for preparing nitrogen-containing silane by catalyzing hydrosilylation reaction of allyl amine compound

Abstract

The invention relates to a method for preparing nitrogen-containing silane by catalyzing hydrosilylation reaction of an allyl amine compound, and belongs to the technical field of organic synthesis. Allylamine and silane are used as raw materials, tris (pentafluorophenyl) boron is used as a catalyst, reaction is performed for 3-24 hours at the temperature of 30-60 DEG C, and a lower Markov addition hydrosilylation product is obtained. The key point for solving the problem is that boron lewis acid activates allylamine to change the polarity of carbon-carbon double bonds, and then the allylamine reacts with silane to obtain an anti-conventional Markov addition hydrosilylation product. The method has the advantages of simple and easily available raw materials, mild reaction conditions, simple operation and wide substrate applicability.

Description

Technical Field

[0001] The invention relates to a method for preparing nitrogen silane, and in particular to a method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of an allylamine compound. Background Art

[0002] Organosilicon compounds are widely used in organic synthesis, organic optoelectronic materials, polymer chemistry and medicinal chemistry (C. Bolm et al., Chem. Soc. Rev. 2013, 42, 8540-8571). Hydrosilylation of olefins is one of the most practical methods for synthesizing organosilicon compounds, and has advantages such as atom economy, so it has always been a hot topic of research.

[0003] Transition metals are the most commonly used catalysts in olefin hydrosilylation reactions. Hydrosilylation reactions catalyzed by metals such as platinum, iron, cobalt, and nickel have the advantages of high selectivity and mild reaction conditions, and have therefore been developed one after another (P. Pawluc et al., ACS Cata l. 2018, 8, 9865-9876). However, there are still problems that need to be solved in this catalytic system, such as the complex structure of the catalyst ligand, which is usually sensitive to air and water; there are metal residues in the product; and it is often accompanied by side reactions such as dehydrogenation silylation, double bond reduction, or olefin isomerization. This reaction also has a problem of regioselectivity, and is usually dominated by anti-Markovnikov addition products.

[0004] The hydrosilylation of olefins without the participation of transition metals is a research difficulty in this field. In 2002, Gevorgyan's research group reported that tri(pentafluorophenyl)borane can be used as a catalyst to activate the silicon-hydrogen bond in silane, realizing the hydrosilylation of substituted olefins and obtaining a series of anti-Markovnikov addition products with high yields (V. Gevorgyan et al., J. Org. Chem. 2002, 67, 1936-1940). In 2015, Chang's research group reported the hydrosilylation of electron-deficient olefin nitrile compounds catalyzed by tri(pentafluorophenyl)borane, which requires four times the equivalent of silane (S. Chang et al., Angew. Chem. Int. Ed. 2015, 54, 6832-6836).

[0005] In summary, the highly selective hydrosilylation of olefins without the participation of transition metals has very important theoretical research value and practical significance for the development of methods for synthesizing organosilicon compounds. This patent hopes to use green and efficient catalysts to achieve the Markovnikov selective hydrosilylation of olefins and provide a method for the precise synthesis of nitrogen-containing silanes. Summary of the invention

[0006] In view of the above problems, the present invention provides a method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of allylamine compounds.

[0007] The present invention adopts the following technical solutions:

[0008] A method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of an allylamine compound, wherein allylamine and silane are used as raw materials, tri(pentafluorophenyl)boron is used as a catalyst, and the mixture is dissolved in a solvent and reacted at 30 to 60° C. for 3 to 24 hours to obtain a Markovnikov addition hydrosilylation product, wherein the general structural formula of the Markovnikov addition hydrosilylation product is as follows:

[0009]

[0010] Among them, R 1 is any one of methyl, ethyl, phenyl, substituted phenyl and benzyl; R 2 is any one of methyl, ethyl, phenyl, substituted phenyl and benzyl; R 3 is any one of H, methyl, ethyl and phenyl, R 4 is any one of methyl and phenyl; R 5 It is any one of H, methyl, substituted phenyl and benzyl.

[0011] Furthermore, the molar ratio of allylamine, silane and tris(pentafluorophenyl)borane is 1:(1-2):(0.01-0.1).

[0012] Furthermore, the general structural formula of the allylamine is as follows:

[0013]

[0014] Furthermore, the general structural formula of the silane is as follows:

[0015]

[0016] Furthermore, the solvent is any one or more of toluene, m-xylene, cyclohexane, dichloromethane, 1,2-dichloroethane and 1,4-dioxane.

[0017] After adopting the above technical solution, the present invention has the following advantages compared with the prior art:

[0018] 1. The present invention utilizes tris(pentafluorophenyl)borane to catalyze the activation of allylamine, thereby changing the polarity of its carbon-carbon double bond, thereby causing a highly selective hydrosilylation reaction to obtain an unconventional Markovnikov addition product. The reaction functional group has a high tolerance and a wide substrate range.

[0019] 2. The catalyst and raw materials of the present invention are simple and easy to obtain, the reaction conditions are mild, the operation is simple, and the atomic utilization rate is high.

[0020] 3. The present invention uses non-metallic catalysts, which can effectively avoid metal residues and reduce environmental pollution.

[0021] The present invention is described in detail below with reference to the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 It is a schematic diagram of the process of the method of the present invention;

[0023] Figure 2 Schematic diagram of the synthesis process of Examples 1-8 of the present invention;

[0024] Figure 3 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 1 of the present invention;

[0025] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 2 of the present invention;

[0026] Figure 5 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 3 of the present invention;

[0027] Figure 6 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 4 of the present invention;

[0028] Figure 7 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 5 of the present invention;

[0029] Figure 8 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 6 of the present invention;

[0030] Fig. 9 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 7 of the present invention;

[0031] Fig.10 This is the hydrogen nuclear magnetic resonance spectrum of the product prepared in Example 8 of the present invention. DETAILED DESCRIPTION

[0032] The principles and features of the present invention are described below in conjunction with the accompanying drawings. The examples given are only used to explain the present invention and are not used to limit the scope of the present invention.

[0033] like Figure 1 As shown, a method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of allylamine compounds, using allylamine and silane as raw materials, tri(pentafluorophenyl)boron as a catalyst, and dissolving them together in a solvent and reacting at 30-60° C. for 3-24 hours to obtain a Markovnikov addition hydrosilylation product, the general structural formula of which is as follows:

[0034]

[0035] Among them, R 1 is any one of methyl, ethyl, phenyl, substituted phenyl and benzyl; R 2is any one of methyl, ethyl, phenyl, substituted phenyl and benzyl; R 3 is any one of H, methyl, ethyl and phenyl, R 4 is any one of methyl and phenyl; R 5 It is any one of H, methyl, substituted phenyl and benzyl.

[0036] The general structural formula of the allylamine is as follows:

[0037]

[0038] The general structural formula of the silane is as follows:

[0039]

[0040] Example 1: Synthesis of N,N-dibenzyl-2-(dimethyl(phenyl)silyl)propan-1-amine:

[0041] like Figure 2 As shown in Figure a, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere. 0.01 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allyldibenzylamine 1a, 0.24 mmol of dimethylphenylsilane 2a and 1 mL of solvent m-xylene were added to the reaction tube in sequence. After sealing, the mixture was stirred continuously at 30°C for 3 hours. After the reaction was completed, 69 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography. The yield was 92%. Figure 3 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product. 1 H NMR(400MHz,Chloroform-d)δ7.59–7.57(m,2H),7.47–7.40(m,11H),7.37–7.33(m 2H),3.88(d,J=13.6Hz,2H),3.38(d,J=13.6Hz,2H),2.57–2.44(m,2H),1.52–1.42(m,1H),1.15(d,J=7.2Hz,3H),0.34(d,J=5.3Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ139.73,138.31,133.81,128.90,128.76,128.02,127.64,126.62,58.03,55.90,17.90,13.04,-4.78,-5.02.HRMS(ESI):m / z Calcd.for[C 25 H 32 NSi + ,M+H]+ :374.2299;Found:374.2297.

[0042] Example 2: N-benzyl-2-(dimethyl(phenyl)silyl)-N-(4-methylbenzyl)

[0043] Synthesis of propan-1-amine

[0044] like Figure 2 As shown in Figure b, in a glove box under an anhydrous inert nitrogen atmosphere, 0.01 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allylamine 1b, 0.24 mmol of dimethylphenylsilane 2a and 1 mL of solvent m-xylene were added to the reaction tube in sequence, and the mixture was sealed and stirred at 30°C for 3 hours. After the reaction was completed, 69 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography, with a yield of 89%. Figure 4 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product. 1 H NMR(400MHz,Chloroform-d)δ7.48–7.45(m,2H),7.39–7.29(m,7H),7.26–7.22(m,3H),7.13(d,J=7.8Hz,2H),3.73(dd,J=13.7 ,7.8Hz,2H),3.24(dd,J=13.7,4.7Hz,2H),2.44–2.31(m,5H),1.40–1.31(m,1H),1.02(d,J=7.3Hz,3H),0.22(d,J=5.6Hz,6H). 13 CNMR(101MHz,Chloroform-d)δ139.84,138.40,136.54,136.07,133.83,128.89,128.85,128.74,128 .71,127.98,127.62,126.56,57.91,57.60,55.82,21.09,17.87,13.02,-4.79,-4.98.HRMS(ESI):m / z Calcd.for[C 26 H 33 NSi + ,M+Na] + :410.2274;Found:410.2272.

[0045] Example 3: Synthesis of N-benzyl-N-(2-(dimethyl(phenyl)silyl)propyl)aniline

[0046] like Figure 2 As shown in Figure c, in a glove box under an anhydrous inert nitrogen atmosphere, 0.01 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allylamine 1c, 0.24 mmol of dimethylphenylsilane 2a and 1 mL of solvent m-xylene were added to the reaction tube in sequence, and the mixture was sealed and stirred at 30°C for 3 hours. After the reaction was completed, 68 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography, with a yield of 95%. Figure 5 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product. 1 H NMR(400MHz,Chloroform-d)δ7.56–7.53(m,2H),7.41–7.38(m,3H),7.30–7.20(m ,3H),7.17–7.11(m,4H),6.64(t,J=7.3Hz,1H),6.57(d,J=8.2Hz,2H),4.60(d,J= 17.2Hz,1H),4.47(d,J=17.1Hz,1H),3.69(dd,J=14.8,3.8Hz,1H),3.19(dd,J=14 .7,11.7Hz,1H),1.68–1.59(m,1H),1.06(d,J=7.2Hz,3H),0.35(d,J=1.3Hz,6H). 13 C NMR(101MHz,Chloroform-d)δ148.39,138.88,137.58,133.88,129.11,128.98,128.45,127.81,126 .58,126.54,115.82,112.63,55.27,53.73,19.35,13.08,-4.69,-5.32.HRMS(ESI):m / zCalcd.for[C 24 H 29 NSi + ,M+Na] + :382.1961;Found:382.1957.

[0047] Example 4: Synthesis of N-(2-(dimethyl(phenyl)silyl)propyl)-N,4-dimethylaniline:

[0048] like Figure 2As shown in Figure d, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere. 0.01 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allylamine 1d, 0.24 mmol of dimethylphenylsilane 2a and 1 mL of solvent m-xylene were added to the reaction tube in sequence. After sealing, the reaction was stirred continuously at 30°C for 12 hours. After the reaction was completed, 52 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography. The yield was 88%. Figure 6 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product. 1 H NMR (400MHz, Chloroform-d) δ7.56–7.54(m,2H),7.42–7.38(m,3H),7.01(d,J=8.8Hz,2H),6.53(d,J=8.6Hz,2H),3.46(dd,J=14 .5,4.2Hz,1H),3.04(dd,J=14.4,11.5Hz,1H),2.86(s,3H),2.26(s,3H),1.55–1.47(m,1H),0.99(d,J=7.3Hz,3H),0.35(s,6H). 13 C NMR(101MHz,Chloroform-d)δ147.63,137.79,133.89,129.51,129.01,127.75,124.84 ,112.47,55.39,39.37,20.16,19.41,12.94,-4.75,-5.19.HRMS(ESI):m / zCalcd.for[C 19 H 28 NSi + ,M+H] + :298.1986;Found:298.1987.

[0049] Example 5: Synthesis of N,N-dibenzyl-2-(dimethyl(phenyl)silyl)-3-phenylpropan-1-amine

[0050] like Figure 2 As shown in Figure e, in a glove box under an anhydrous inert nitrogen atmosphere, 0.02 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allylamine 1e, 0.24 mmol of dimethylphenylsilane 2a and 1 mL of solvent m-xylene were added to the reaction tube in sequence, and the mixture was sealed and stirred at 60°C for 24 hours. After the reaction was completed, 41 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography, with a yield of 46%. Figure 7 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product.1 H NMR(400MHz,Chloroform-d)δ7.38–7.35(m,2H),7.33–7.10(m,16H),7.03–7.00(m,2H),3.54(d,J=13.5Hz,2H),3.27(d,J=13.5Hz,2H ),2.81(dd,J=14.1,6.8Hz,1H),2.53(dd,J=14.1,7.0Hz,1H),2.43(d,J=7.6Hz,2H),1.64(p,J=7.3Hz,1H),0.13(s,3H),0.03(s,3H). 13 C NMR(101MHz,Chloroform-d)δ142.86,139.29,138.51,133.85,129.25,128.95,128.72,128.0 7,128.03,127.64,126.75,125.49,58.17,54.76,34.72,26.06,-3.73,-4.09.HRMS(ESI):m / z Calcd.for[C 31 H 36 NSi + ,M+H] + :450.2612;Found:450.2606.

[0051] Example 6: Synthesis of N,N-dibenzyl-2-(dimethyl(p-tolyl)silyl)propan-1-amine Figure 2 As shown in Figure f, in a glove box under an anhydrous inert nitrogen atmosphere, 0.01 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allylamine 1a, 0.24 mmol of silane 2b and 1 mL of solvent m-xylene were added to the reaction tube in sequence, and the mixture was sealed and stirred continuously at 30°C for 3 hours. After the reaction was completed, 75 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography, with a yield of 96%. Figure 8 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product. 1H NMR (400MHz, Chloroform-d) δ7.42–7.34(m,10H),7.30–7.26(t,J=6.9Hz,2H),7.23(d,J=7.5Hz,2H),3.81(d,J=13. 7Hz, 2H), 3.31 (d, J = 13.7Hz, 2H), 2.50–2.37 (m, 5H), 1.43–1.34 (m, 1H), 1.07 (d, J = 7.2Hz, 3H), 0.25 (d, J = 5.3Hz, 6H). 13 C NMR(101MHz,Chloroform-d)δ139.81,138.53,134.65,133.88,128.91,128.50,1 28.01,126.61,58.06,55.99,21.43,17.97,13.04,-4.69,-4.92.HRMS(ESI):m / z Calcd.for[C 26 H 34 NSi + ,M+H] + :388.2455;Found:388.2454.

[0052] Example 7: Synthesis of N-(2-(benzyldimethylsilyl)propyl)-N,4-dimethylaniline Figure 2 As shown in Figure g, in a glove box under an anhydrous inert nitrogen atmosphere, 0.01 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allylamine 1d, 0.24 mmol of silane 2c and 1 mL of solvent m-xylene were added to the reaction tube in sequence, and the mixture was sealed and stirred continuously at 30°C for 12 hours. After the reaction was completed, 37 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography, with a yield of 59%. Fig. 9 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product. 1 H NMR(400MHz,Chloroform-d)δ7.26–7.22(m,2H),7.12–7.08(m,1H),7.04(d,J=7.8Hz,4H),6.60(d,J=8.1Hz,2H),3.41(dd,J=14.3,4.5Hz,1H), 3.08(dd,J=14.3,11.6Hz,1H),2.88(s,3H),2.26(s,3H),2.16(d,J=2.0 Hz,2H),1.40–1.30(m,1H),0.97(d,J=7.3Hz,3H),0.02(d,J=4.0Hz,6H). 13C NMR(101MHz,Chloroform-d)δ147.88,139.96,129.57,128.24,128.19,125.04,124. 07,112.63,55.32,39.11,23.89,20.18,18.62,12.70,-5.03,-5.15.HRMS(ESI):m / z Calcd.for[C 20 H 29 NSi + ,M+Na] + :334.1961;Found:334.1956.

[0053] Example 8: Synthesis of N-benzyl-2-(diphenylsilyl)-N-methylpropan-1-amine

[0054] like Figure 2 As shown in Figure h, in a glove box under an anhydrous inert nitrogen atmosphere, 0.02 mmol of tri(pentafluorophenyl)borane, 0.2 mmol of allylamine 1e, 0.24 mmol of diphenylsilane 2d and 1 mL of solvent m-xylene were added to the reaction tube in sequence, and the mixture was sealed and stirred at 50°C for 24 hours. After the reaction was completed, 45 mg of the target product (colorless liquid) was obtained after purification by silica gel column chromatography, with a yield of 66%. Fig.10 As shown, it can be seen that this embodiment can successfully synthesize the corresponding Markovnikov addition product. 1 H NMR(400MHz,Chloroform-d)δ7.52–7.51(m,4H),7.33–7.24(m,6H),7.20–7.11(m,5H),4.74(d,J=2.5Hz,1H),3.43( d,J=13.1Hz,1H),3.25(d,J=13.1Hz,1H),2.41–2.31(m,2H),1.99(s,3H),1.74–1.64(m,1H),1.04(d,J=7.3Hz,3H). 13 C NMR(101MHz,Chloroform-d)δ139.43,135.64,135.54,133.76,133.54,129.41,128.9 1,128.05,127.89,127.84,126.70,62.20,61.05,41.96,16.69,13.86.HRMS(ESI):m / z Calcd.for[C 23 H 28 NSi + ,M+H] +:346.1986;Found:346.1984.

[0055] In summary, the embodiment of the present invention provides a method for preparing nitrogen-containing silane by hydrosilylation of allylamine, by reacting olefin and silane in a solvent in the presence of a catalyst, the synthesis of the target product nitrogen-containing silane can be successfully achieved.

[0056] The above is an example of the best implementation of the present invention, and the parts not described in detail are common knowledge of ordinary technicians in the field. The protection scope of the present invention shall be based on the content of the claims, and any equivalent transformation based on the technical enlightenment of the present invention is also within the protection scope of the present invention.

Claims

1. A method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of an allylamine compound, characterized in that: Allylamine and silane are used as raw materials, tri(pentafluorophenyl)borane is used as a catalyst, and they are dissolved in a solvent and reacted at 30 to 60° C. for 3 to 24 hours to obtain a Markovnikov addition hydrosilylation product. The general structural formula of the Markovnikov addition hydrosilylation product is as follows: Among them, R 1 is any one of methyl, ethyl, phenyl, substituted phenyl and benzyl; R 2 is any one of methyl, ethyl, phenyl, substituted phenyl and benzyl; R 3 is any one of H, methyl, ethyl and phenyl, R 4 is any one of methyl and phenyl; R 5 It is any one of H, methyl, substituted phenyl and benzyl.

2. The method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of allylamine compounds according to claim 1, characterized in that: The molar ratio of allylamine, silane and tris(pentafluorophenyl)borane is 1:(1-2):(0.01-0.1).

3. The method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of allylamine compounds according to claim 1, characterized in that: The general structural formula of the allylamine is as follows:

4. The method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of allylamine compounds according to claim 1, characterized in that: The general structural formula of the silane is as follows:

5. The method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of allylamine compounds according to claim 1, characterized in that: The solvent is any one or more of toluene, m-xylene, cyclohexane, dichloromethane, 1,2-dichloroethane and 1,4-dioxane.

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