CN119528963A - A method for preparing nitrogen-containing silane by catalyzing the hydrosilylation reaction of allylamine compounds - Google Patents

Abstract

The invention relates to a method for preparing nitrogen-containing silane by catalyzing hydrosilation reaction of allylamine compounds, belonging to the technical field of organic synthesis. According to the invention, allylamine and silane are used as raw materials, tris (pentafluorophenyl) boron is used as a catalyst, and the reaction is carried out for 3-24 hours at the temperature of 30-60 ℃ to obtain a lower Mahalanobis addition hydrosilation product. The main point of the solution is that boron Lewis acid activates allylamine to change the polarity of carbon-carbon double bond, and then reacts with silane to obtain the anti-conventional Marshall addition hydrosilation product. The invention has the advantages of simple and easily obtained raw materials, mild reaction conditions, simple operation and wide substrate applicability.

Description

Method for preparing nitrogen-containing silane by catalyzing hydrosilation reaction of allylamine compound

Technical Field

The invention relates to a preparation method of nitrogen silane, in particular to a method for preparing nitrogen silane by catalyzing hydrosilation of allylamine compounds.

Background

Organosilicon compounds are widely used in the fields of organic synthesis, organic photoelectric materials, polymer chemistry, pharmaceutical chemistry, etc. (C.Bolm et al, chem. Soc. Rev.2013,42, 8540-8571). The hydrosilation of olefins is one of the most practical methods for synthesizing organosilicon compounds, and has the advantages of atom economy and the like, and therefore has been a hot spot of research.

Transition metals are the most commonly used catalysts in olefin hydrosilation reactions, and metal-catalyzed hydrosilation reactions of platinum, iron, cobalt, nickel, etc. have the advantages of high selectivity, mild reaction conditions, etc., and thus have been developed successively (p.pawluc et al, ACS catalyst.2018, 8, 9865-9876). However, the catalyst system still has the problems to be solved, such as complex structure of the catalyst ligand, general sensitivity to air and water, metal residue in the product, and side reactions such as dehydrogenation and siliconization, double bond reduction or olefin isomerization, etc. The reaction also has regioselectivity problems, usually based on anti-mahalanobis addition products.

The hydrosilation of olefins without the participation of transition metals is a research difficulty in this field. The Gevorgyan group of problems in 2002 reported that tris (pentafluorophenyl) borane can act as a catalyst to activate the silicon-hydrogen bond in silanes, effecting the hydrosilation of substituted olefins, and obtaining a series of anti-mahalanobis adducts in higher yields (v. Gevorgyan et al, j. Org. Chem.2002,67, 1936-1940). In 2015, the Chang group reported that tris (pentafluorophenyl) borane catalyzes the hydrosilation of electron deficient dinitrile compounds, which requires four equivalents of silane (S.Chang et al, angew.chem. Int. Ed.2015,54, 6832-6836).

In conclusion, the olefin high-selectivity hydrosilation reaction without participation of transition metal has very important theoretical research value and practical significance for the development of an organosilicon compound synthesis method. The patent hopes to realize the Marsh-selective hydrosilation reaction of olefin by using a green and efficient catalyst, and provides a method for the accurate synthesis of nitrogen-containing silane.

Disclosure of Invention

In view of the above problems, the present invention provides a method for preparing nitrogen-containing silanes by catalyzing hydrosilation of allylamine compounds.

The invention adopts the following technical scheme:

A method for preparing nitrogen-containing silane by catalyzing hydrosilation reaction of allylamine compound takes allylamine and silane as raw materials, tris (pentafluorophenyl) boron as a catalyst, and the raw materials are dissolved in a solvent together and then react for 3-24 hours at 30-60 ℃ to obtain a Marshall addition hydrosilation product, wherein the Marshall addition hydrosilation product has the following structural general formula:

Wherein 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, and R ⁵ is any one of H, methyl, substituted phenyl and benzyl.

Further, the mass ratio of allylamine, silane and tris (pentafluorophenyl) boron is 1 (1-2): 0.01-0.1.

Further, the structural general formula of the allylamine is as follows:

Further, the structural general formula of the silane is as follows:

further, the solvent is any one or more of toluene, m-xylene, cyclohexane, methylene dichloride, 1, 2-dichloroethane and 1, 4-dioxane.

After the technical scheme is adopted, compared with the prior art, the invention has the following advantages:

1. The invention uses tri (pentafluorophenyl) borane to catalyze and activate allylamine to change the polarity of carbon-carbon double bond, thereby generating hydrosilation reaction with high selectivity to obtain the anti-conventional Mahalanobis addition product. The tolerance of the reaction functional group is high, and the substrate range is wide.

2. The catalyst and the raw materials are simple and easy to obtain, the reaction condition is mild, the operation is simple and convenient, and the atom utilization rate is high.

3. The invention uses non-metal catalyst, which can effectively avoid metal residue and reduce environmental pollution.

The invention will now be described in detail with reference to the drawings and examples.

Drawings

FIG. 1 is a schematic diagram of the process of the method of the present invention;

FIG. 2 is a schematic diagram of the synthesis process of examples 1-8 of the present invention;

FIG. 3 is a chart showing the nuclear magnetic resonance hydrogen spectrum of the product prepared in example 1 of the present invention;

FIG. 4 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product prepared in example 2 of the present invention;

FIG. 5 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product prepared in example 3 of the present invention;

FIG. 6 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product prepared in example 4 of the present invention;

FIG. 7 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product prepared in example 5 of the present invention;

FIG. 8 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product prepared in example 6 of the present invention;

FIG. 9 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product prepared in example 7 of the present invention;

FIG. 10 is a chart showing the hydrogen nuclear magnetic resonance spectrum of the product prepared in example 8 of the present invention.

Detailed Description

The principles and features of the present invention are described below with reference to the drawings, the examples are illustrated for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.

As shown in figure 1, in the method for preparing nitrogen-containing silane by catalyzing hydrosilation reaction of allylamine compound, allylamine and silane are used as raw materials, tris (pentafluorophenyl) boron is used as a catalyst, and after being dissolved in a solvent together, the mixture is reacted for 3 to 24 hours at a temperature of 30 to 60 ℃ to obtain a Marshall addition hydrosilation product, and the Marshall addition hydrosilation product has a structural general formula as follows:

Wherein 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, and R ⁵ is any one of H, methyl, substituted phenyl and benzyl.

The structural general formula of the allylamine is as follows:

the structural general formula of the silane is as follows:

EXAMPLE 1 Synthesis of N, N-dibenzyl-2- (dimethyl (phenyl) silyl) propan-1-amine:

As shown in a diagram of FIG. 2, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere, 0.01mmol of tris (pentafluorophenyl) borane, 0.2mmol of allyldibenzylamine 1a, 0.24mmol of dimethylphenylsilane 2a and 1mL of solvent meta-xylene were sequentially added to the reaction tube, and after the completion of the reaction, the reaction was continuously stirred at 30℃for 3 hours, and after the completion of the reaction, 69mg (colorless liquid) of the objective product was obtained after purification by silica gel column chromatography in 92% yield. As shown in FIG. 3, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis addition product ,¹H 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).¹³C 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[C₂₅H₃₂NSi⁺,M+H]⁺:374.2299;Found:374.2297.

EXAMPLE 2N-Benzyl-2- (dimethyl (phenyl) silyl) -N- (4-methylbenzyl)

Propan Synthesis of 1-amine

As shown in a diagram b of FIG. 2, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere, 0.01mmol of tris (pentafluorophenyl) borane, 0.2mmol of allylamine 1b, 0.24mmol of dimethylphenylsilane 2a and 1mL of solvent meta-xylene were sequentially added to the reaction tube, the mixture was continuously stirred at 30℃for 3 hours after sealing, and after completion of the reaction, 69mg (colorless liquid) of the objective product was obtained after purification by silica gel column chromatography in 89% yield. As shown in FIG. 4, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis addition product ,¹H 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).¹³C NMR(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[C₂₆H₃₃NNaSi⁺,M+Na]⁺:410.2274;Found:410.2272.

Example 3:N Synthesis of Benzyl-N- (2- (dimethyl (phenyl) silyl) propyl) aniline

As shown in the graph C in FIG. 2, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere, 0.01mmol of tris (pentafluorophenyl) borane, 0.2mmol of allylamine 1C, 0.24mmol of dimethylphenylsilane 2a and 1mL of solvent meta-xylene were sequentially added to the reaction tube, and after the sealing, stirring was continued for 3 hours at 30℃and after the completion of the reaction, 68mg (colorless liquid) of the objective product was obtained after purification by silica gel column chromatography in 95% yield. As shown in FIG. 5, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis addition product ,¹H 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).¹³C 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/z Calcd.for[C₂₄H₂₉NNaSi⁺,M+Na]⁺:382.1961;Found:382.1957.

Example 4 Synthesis of N- (2- (dimethyl (phenyl) silyl) propyl) -N, 4-DIMETHYLANILINE:

As shown in the graph d in FIG. 2, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere, 0.01mmol of tris (pentafluorophenyl) borane, 1d of allylamine, 0.2mmol of dimethylphenylsilane 2a, 0.24mmol of solvent m-xylene and 1mL of solvent were sequentially added to the reaction tube, and after the completion of the reaction, the reaction was continuously stirred at 30℃for 12 hours, and after the completion of the reaction, 52mg (colorless liquid) of the objective product was obtained after purification by silica gel column chromatography in 88% yield. As shown in FIG. 6, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis addition product ,¹H 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).¹³C 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/z Calcd.for[C₁₉H₂₈NSi⁺,M+H]⁺:298.1986;Found:298.1987.

EXAMPLE 5 Synthesis of N, N-dibenzyl-2- (dimethyl (phenyl) silyl) -3-phenylpropan-1-amine

As shown in FIG. 2 e, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere, 0.02mmol of tris (pentafluorophenyl) borane, 0.2mmol of allylamine 1e, 0.24mmol of dimethylphenylsilane 2a and 1mL of solvent meta-xylene were sequentially added to the reaction tube, and the mixture was continuously stirred at 60℃for 24 hours after sealing, and after completion of the reaction, 41mg (colorless liquid) of the objective product was obtained after purification by silica gel column chromatography in 46% yield. As shown in FIG. 7, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis addition product ,¹H 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).¹³C NMR(101MHz,Chloroform-d)δ142.86,139.29,138.51,133.85,129.25,128.95,128.72,128.07,128.03,127.64,126.75,125.49,58.17,54.76,34.72,26.06,-3.73,-4.09.HRMS(ESI):m/z Calcd.for[C₃₁H₃₆NSi⁺,M+H]⁺:450.2612;Found:450.2606.

EXAMPLE 6 Synthesis of N, N-dibenzyl-2- (dimethyl (p-tolyl) silyl) propan-1-amine As shown in figure 2 f, the procedure was carried out in a glove box under anhydrous inert nitrogen atmosphere, 0.01mmol of tris (pentafluorophenyl) borane, 0.2mmol of allylamine 1a, 0.24mmol of silane 2b and 1mL of solvent meta-xylene were added sequentially to the reaction tube, and stirring was continued for 3 hours at 30℃after sealing, after the reaction was completed, 75mg of the desired product (colorless liquid) was obtained after purification by silica gel column chromatography in 96% yield. As shown in FIG. 8, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis 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).¹³C NMR(101MHz,Chloroform-d)δ139.81,138.53,134.65,133.88,128.91,128.50,128.01,126.61,58.06,55.99,21.43,17.97,13.04,-4.69,-4.92.HRMS(ESI):m/z Calcd.for[C₂₆H₃₄NSi⁺,M+H]⁺:388.2455;Found:388.2454.

EXAMPLE 7 Synthesis of N- (2- (benzyldimethylsilyl) propyl) -N,4-DIMETHYLANILINE As shown in the g chart in FIG. 2, in a glove box under an anhydrous inert nitrogen atmosphere, 0.01mmol of tris (pentafluorophenyl) borane, 0.2mmol of allylamine 1d, 0.24mmol of silane 2C and 1mL of meta-xylene as solvents were sequentially added to a reaction tube, and after sealing, stirring was continued for 12 hours at 30℃and after completion of the reaction, 37mg (colorless liquid) of the objective product was obtained after purification by silica gel column chromatography in 59% yield. As shown in FIG. 9, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis addition product ,¹H 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＝2.0Hz,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[C₂₀H₂₉NNaSi⁺,M+Na]⁺:334.1961;Found:334.1956.

EXAMPLE 8 Synthesis of N-benzoyl-2- (DIPHENYLSILYL) -N-methylpropan-1-amine

As shown in the h chart of FIG. 2, the reaction was carried out in a glove box under an anhydrous inert nitrogen atmosphere, 0.02mmol of tris (pentafluorophenyl) borane, 0.2mmol of allylamine 1e, 2d of diphenylsilane, 0.24mmol of solvent m-xylene, 1mL of the solvent were sequentially added to the reaction tube, the mixture was continuously stirred at 50℃for 24 hours after the sealing, and 45mg (colorless liquid) of the objective product was obtained after purification by silica gel column chromatography in 66% yield. As shown in FIG. 10, it can be seen that the present example successfully synthesizes the corresponding Mahalanobis addition product ,¹H 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).¹³C NMR(101MHz,Chloroform-d)δ139.43,135.64,135.54,133.76,133.54,129.41,128.91,128.05,127.89,127.84,126.70,62.20,61.05,41.96,16.69,13.86.HRMS(ESI):m/z Calcd.for[C₂₃H₂₈NSi⁺,M+H]⁺:346.1986;Found:346.1984.

In summary, the embodiment of the invention provides a method for preparing nitrogen-containing silane through allylamine hydrosilation, which utilizes the reaction of olefin and silane in a solvent in the presence of a catalyst, and can successfully realize the synthesis of the target product nitrogen-containing silane.

The foregoing is illustrative of the best mode of carrying out the invention, and is not presented in any detail as is known to those of ordinary skill in the art. The protection scope of the invention is defined by the claims, and any equivalent transformation based on the technical teaching of the invention is also within the protection scope of the invention.

Claims (5)

1. A method for preparing nitrogen-containing silane by catalyzing hydrosilation reaction of allylamine compounds is characterized in that allylamine and silane are used as raw materials, tris (pentafluorophenyl) boron is used as a catalyst, and after being dissolved in a solvent together, the mixture is reacted for 3-24 hours at a temperature of 30-60 ℃ to obtain a Marshall addition hydrosilation product, and the Marshall addition hydrosilation product has a structural general formula as follows:

Wherein 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, and R ⁵ is any one of H, methyl, substituted phenyl and benzyl.

2. The method for preparing nitrogen-containing silane by catalyzing hydrosilation of allylamine compound according to claim 1, wherein the mass ratio of allylamine, silane and tris (pentafluorophenyl) boron is 1 (1-2): 0.01-0.1.

3. The method for preparing nitrogen-containing silane by catalyzing hydrosilation of allylamine compound according to claim 1, wherein the allylamine has the following structural formula:

4. The method for preparing nitrogen-containing silane by catalyzing hydrosilation of allylamine compound according to claim 1, wherein the silane has the following structural formula:

5. The method for preparing nitrogen-containing silane by catalyzing hydrosilation of allylamine compound according to claim 1, wherein the solvent is any one or more of toluene, meta-xylene, cyclohexane, methylene chloride, 1, 2-dichloroethane and 1, 4-dioxane.