Method for catalyzing dehydrogenation oxidation of alcohol by using carbonyl manganese

Abstract

The invention relates to the technical field of synthesis of organic compounds, in particular to a method for catalyzing dehydrogenation and oxidation of alcohol by using manganese carbonyl, and particularly relates to a method for preparing a series of carbonyl-containing compounds by using manganese carbonyl as a catalyst and co-catalyzing dehydrogenation and oxidation reaction of alcohol compounds with small-molecular thiophenol and silane. The manganese carbonyl catalyst adopted in the invention is a commercially available cheap metal catalyst, and has good biological friendliness; the method realizes dehydrogenation and oxidation of alcohol compounds under mild conditions, the byproduct is hydrogen, the reaction is more green and environment-friendly, and the adaptability is wider. Different types of aldehyde ketone compounds can be efficiently synthesized through the same catalytic system, and a more practical universal path is provided for synthesis of the aldehyde ketone compounds.

Description

Technical Field

[0001] The present invention relates to the technical field of organic compound synthesis, and particularly relates to a method for catalytic dehydrogenation of alcohols with manganese carbonyl. Background Art

[0002] The oxidation of alcohols is one of the most fundamental and important reactions in organic chemistry and industrial catalysis. Through the continuous efforts of chemists, many oxidation methods for alcohols have been discovered and reported. Although there are many means, these traditional oxidation methods have certain problems, and it is imperative to develop a more economical and efficient catalytic oxidation method for alcohols.

[0003] The catalytic oxidation process of alcohols has been fully developed in the past few decades. Currently, the research mainly focuses on the dehydrogenation of alcohol compounds catalyzed by transition metals to prepare aldehyde and ketone compounds. For example, the Li Jun research group reported in 2016 that Pd0 was immobilized on surface-modified SBA-15 by in-situ H2 reduction to synthesize an efficient dehydrogenation catalyst. Under normal pressure of nitrogen and using water as a solvent, various aromatic alcohols such as vanillyl alcohol can achieve dehydrogenation oxidation in this system, as Figure 1 shown, but this synthesis method uses expensive metal palladium and reacts at reflux temperature, so it is not economical and has poor biocompatibility;

[0004] The Lee research group reported in 2017 that water-soluble Rh nanoparticles were synthesized in a cetyltrimethylammonium bromide / ionic liquid-micelle system. These nanoparticles and NaBH4 have high catalytic activity for the acceptorless dehydrogenation reaction of various primary and secondary aromatic alcohols in H2O, as Figure 2 shown, but this synthesis method uses expensive metal Rh and NaBH4, is not economical and the reaction conditions are relatively severe;

[0005] The Muthaiah research group reported a (PNP)Ru(II) complex in 2018. In the presence of KOBu t this complex showed good alcohol dehydrogenation activity in the medium, as Figure 3 shown in a. In this system, a series of primary and secondary aromatic alcohols can be converted into the corresponding aldehydes and ketones in good to moderate yields, while the conversion rate of fatty alcohols decreases slightly; in 2020, this research group further reported three in-situ catalytic systems formed by commercially available [Ru(benzene)Cl2]2, [Ru(COD)Cl2] n and [Ru(p-cymene)Cl2]2 combined with hexamethylenetetramine, all of which achieved the oxidation of secondary alcohols with very high atom economy, as Figure 3 shown in b. However, the above two synthesis methods both use expensive metal Ru, and there are problems such as long reaction time, high reaction temperature, and the need for additives, and they are not green and environmentally friendly.

[0006] The Kimura research group reported a dehydrogenation strategy for primary alcohols catalyzed by the Pd / Xantphos catalytic system in 2019. As Figure 4 shown, for aromatic alcohols, the electronic properties and positions of substituents on the aromatic ring have a significant impact on the reaction efficiency; while the reaction efficiency of alkyl alcohols in this system is relatively low. However, this synthetic method also uses expensive palladium metal.

[0007] In summary, although the development of various transition metal catalytic systems has effectively promoted the development of alcohol dehydrogenation, many problems still remain. First of all, most catalytic systems rely on noble metal complexes, which pose great challenges in terms of economy and operability; secondly, since the dehydrogenation of alcohols is thermodynamically unfavorable, most reactions require harsh conditions. Finally, most of these catalytic systems can only achieve the oxidation of benzyl alcohol compounds, and most catalytic systems have poor dehydrogenation effects on alkyl alcohols. Therefore, it is very necessary to develop a more general and inexpensive metal-catalyzed efficient dehydrogenation strategy for alcohol compounds.

[0008] Therefore, according to the related technologies described above, there is an urgent need to develop a method for the dehydrogenation of alcohols catalyzed by manganese carbonyl. Summary of the Invention

[0009] In view of this, the purpose of the present invention is to provide a method for the dehydrogenation of alcohols catalyzed by manganese carbonyl, so as to provide a method with green environmental protection, wide adaptability, high reaction efficiency and simple reaction operation.

[0010] Based on the above purpose, the present invention provides a method for the dehydrogenation of alcohols catalyzed by manganese carbonyl.

[0011] A method for the dehydrogenation of alcohols catalyzed by manganese carbonyl includes a method for the synthesis of aldehyde compounds and a method for the synthesis of ketone compounds.

[0012] Preferably, the method for the synthesis of aldehyde compounds is as follows:

[0013] Add dimanganese decacarbonyl, a hydrogen positive donor and a hydrogen negative donor to the primary alcohol substrate, and react in an organic solvent under an inert gas atmosphere at 60 - 80 °C for 24 - 48 h. After column chromatography separation, aldehyde compounds are obtained.

[0014] Preferably, the structural formula of the primary alcohol substrate is as follows:

[0015] Among them, the R1 group is an aryl group; the R2 group is a hydrogen atom.

[0016] Furthermore, the primary alcohol is m-nitrobenzyl alcohol and p-methoxybenzyl alcohol.

[0017] Furthermore, the structural formula of the m-nitrobenzyl alcohol is as follows:

[0018]

[0019] Furthermore, the structural formula of the p-methoxybenzyl alcohol is as follows:

[0020]

[0021] Preferably, the synthesis method of the ketone compound is as follows:

[0022] Add manganese decacarbonyl, a hydrogen positive donor, and a hydrogen negative donor to the secondary alcohol substrate, and react in an organic solvent under an inert gas atmosphere at 60 - 80 °C for 24 - 48 h. After column chromatography separation, the ketone compound is obtained.

[0023] Preferably, the structural formula of the secondary alcohol is as follows:

[0024] Wherein the R1 group is an aryl group; the R2 group is any one of an aryl group and an alkyl group.

[0025] Furthermore, the secondary alcohol is any one of 1-(2-naphthyl)ethanol, 3-chlorobenzhydrol, and α-cyclopropylbenzyl alcohol.

[0026] Furthermore, the structural formula of the 1-(2-naphthyl)ethanol is as follows:

[0027]

[0028] Furthermore, the structural formula of the 3-chlorobenzhydrol is as follows:

[0029]

[0030] Furthermore, the structural formula of the α-cyclopropylbenzyl alcohol is as follows:

[0031]

[0032] Preferably, the hydrogen positive donor is any one of p-chlorothiophenol, p-nitrothiophenol, and p-methylthiophenol.

[0033] Preferably, the molar percentage of the hydrogen positive donor and benzyl alcohol is 15% - 35%.

[0034] Preferably, the hydrogen negative donor is any one of triethylsilane and triisopropylsilane.

[0035] Preferably, the molar percentage of the hydrogen negative donor and benzyl alcohol is 15% - 35%.

[0036] Preferably, the molar percentage of the dimanganese decacarbonyl and benzyl alcohol is 5%-15%.

[0037] Preferably, the organic solvent is any one of tetrahydrofuran, acetonitrile, toluene, and N,N-dimethylformamide.

[0038] Preferably, the inert gas includes but is not limited to nitrogen.

[0039] In the present invention, a benzyl alcohol compound is used as the starting material, and dimanganese decacarbonyl is used as a catalyst to efficiently catalyze the dehydrogenation of a series of benzyl alcohols in the presence of a hydrogen positive donor thiophenol and a hydrogen negative donor silane to respectively synthesize aldehyde and ketone compounds with high synthetic value and high biological activity. Aldehyde and ketone compounds are important chemical intermediates and are widely used in the synthesis and production of pharmaceuticals, dyes, and agrochemicals. For example, aldehyde and ketone compounds are important raw materials for manufacturing plastics, dyes, and solvents, and are also the main components of many drugs and antibacterial agents.

[0040] Advantages of the present invention:

[0041] The present invention provides a method for catalytic dehydrogenation of alcohols with manganese carbonyl. Using dimanganese decacarbonyl as a catalyst, a method for dehydrogenating a series of benzyl alcohols in the presence of a hydrogen positive donor thiophenol and a hydrogen negative donor silane to prepare aldehyde and ketone compounds. The operation of the present invention is simple, the raw materials are easy to obtain, the post-treatment is simple, the reaction is efficient and diverse. The catalyst dimanganese decacarbonyl used in the present invention is a commercially available metal catalyst. Compared with the noble metal catalysts used in the previous dehydrogenation of alcohols, it is cheap and has good biocompatibility. In the presence of the catalyst, the dehydrogenation of alcohol compounds is realized under mild conditions. The system does not require the participation of ligands or additives, the reaction is more environmentally friendly, and the adaptability is wider. The present invention can efficiently synthesize different types of aldehyde and ketone compounds through the same catalytic system, providing a more practical and universal route for the synthesis of aldehyde and ketone compounds. Description of the drawings

[0042] In order to more clearly illustrate the technical solutions in the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are only those of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative efforts.

[0043] Figure 1 It is a reaction process diagram and a catalyst schematic diagram reported by the Li Jun research group in 2016 for realizing the dehydrogenation of various aromatic alcohols by fixing Pd0 on surface-modified SBA-15;

[0044] Figure 2It is the reaction process diagram of the acceptorless dehydrogenation of various primary and secondary aromatic alcohols using water-soluble Rh nanoparticles reported by the Lee research group in 2017;

[0045] Figure 3 a is the reaction process diagram and the schematic diagram of the complex for the dehydrogenation of alcohols catalyzed by the (PNP)Ru(II) complex reported by the Muthaiah research group in 2018;

[0046] Figure 3 b is the reaction process diagram and the schematic diagram of the catalyst for the oxidation of secondary alcohols catalyzed by three in-situ catalytic systems formed by commercially available [Ru(benzene)Cl2]2, [Ru(COD)Cl2] n and [Ru(p-cymene)Cl2]2 combined with hexamethylenetetramine reported by the Muthaiah research group in 2020;

[0047] Figure 4 It is the dehydrogenation oxidation strategy diagram of primary alcohols catalyzed by the Pd / Xantphos catalytic system reported by the Kimura research group in 2019;

[0048] Figure 5 It is the reaction process diagram for catalyzing the synthesis of m-nitrobenzaldehyde from m-nitrobenzyl alcohol in Example 1;

[0049] Figure 6 It is the 1H NMR spectrum of m-nitrobenzaldehyde prepared in Example 1;

[0050] Figure 7 It is the 13C NMR spectrum of m-nitrobenzaldehyde prepared in Example 1;

[0051] Figure 8 It is the reaction process diagram for catalyzing the synthesis of p-methoxybenzaldehyde from p-methoxybenzyl alcohol in Example 2;

[0052] Figure 9 It is the 1H NMR spectrum of p-methoxybenzaldehyde prepared in Example 2;

[0053] Figure 10 It is the 13C NMR spectrum of p-methoxybenzaldehyde prepared in Example 2;

[0054] Figure 11 It is the reaction process diagram for catalyzing the synthesis of 2-naphthyl ethyl ketone from 1-(2-naphthyl) ethanol in Example 3;

[0055] Figure 12 It is the 1H NMR spectrum of 2-naphthyl ethyl ketone prepared in Example 3;

[0056] Figure 13 It is the 13C NMR spectrum of 2-naphthyl ethyl ketone prepared in Example 3;

[0057] Figure 14 It is the reaction process diagram for catalyzing the synthesis of 3-chlorobenzophenone from 3-chlorodiphenylmethanol in Example 4;

[0058] Figure 15 It is the 1H NMR spectrum of 3-chlorobenzophenone prepared in Example 4;

[0059] Figure 16 It is the 13C NMR spectrum of 3-chlorobenzophenone prepared in Example 4;

[0060] Figure 17 It is the reaction process diagram for catalyzing the synthesis of phenylcyclopropyl ketone from α-cyclopropylbenzyl alcohol in Example 5;

[0061] Figure 18 It is the 1H NMR spectrum of phenylcyclopropyl ketone prepared in Example 5;

[0062] Figure 19 It is the 13C NMR spectrum of phenylcyclopropyl ketone prepared in Example 5. Detailed implementation manners

[0063] To make the objectives, technical solutions and advantages of the present invention clearer and more understandable, the present invention will be further described in detail below in conjunction with specific embodiments.

[0064] Example 1: As Figure 5 shown, the process of catalyzing the synthesis of m-nitrobenzaldehyde from m-nitrobenzyl alcohol is as follows:

[0065] S1. Place 31.2 mg of m-nitrobenzyl alcohol, 8.8 mg of decacarbonyldimanganese, and 5.1 mg of p-methylthiophenol in a 25 mL reaction tube. After displacing nitrogen three times, add 2 mL of N,N-dimethylformamide as a solvent under a nitrogen stream, and then add 4.3 mg of triethylsilane. Tighten the bottle cap, raise the reaction temperature to 80 °C, and after reacting for 48 h, remove the solvent. The white solid m-nitrobenzaldehyde is obtained by column chromatography separation, and its nuclear magnetic resonance data is 1 HNMR(400MHz,Chloroform-d)δ10.13(s,1H),8.72(s,1H),8.49(d,J=9.4Hz,1H),8.24(d,J=7.7Hz,1H),7.77(t,J=7.9Hz,1H). 13 C NMR(101MHz,Chloroform-d)δ189.54,137.22,134.44,130.21,128.43,124.35, and the nuclear magnetic resonance spectra are as Figure 6 and Figure 7As shown, the mass of the obtained m-nitrobenzaldehyde is 24.5 mg, and the yield is 81%.

[0066] Example 2: As Figure 8 shown, the process of catalyzing the synthesis of p-methoxybenzaldehyde from p-methoxybenzyl alcohol is as follows:

[0067] 27.1 mg of p-methoxybenzyl alcohol, 8.9 mg of dimanganese decacarbonyl, and 5.3 mg of p-methylbenzenethiol were placed in a 25 mL reaction tube. After displacing nitrogen three times, 2 mL of N,N-dimethylformamide was added as a solvent under a nitrogen stream, and then 4.4 mg of triethylsilane was added. The bottle stopper was tightened, the reaction temperature was raised to 80 °C, and after reacting for 36 h, the solvent was removed. The yellow solid p-methoxybenzaldehyde was obtained by column chromatography separation, and the nuclear magnetic resonance data was 1 1H NMR (400 MHz, Chloroform-d) δ 9.88 (s, 1H), 7.84 (d, J = 8.8 Hz, 2H), 7.00 (d, J = 8.7 Hz, 2H), 3.89 (s, 3H). 13 13C NMR (101 MHz, Chloroform-d) δ 190.97, 164.75, 132.13, 130.09, 114.45, 55.72. The nuclear magnetic resonance spectrum is as Figure 9 and Figure 10 shown, where the mass of the obtained p-methoxybenzaldehyde is 20.3 mg, and the yield is 76%.

[0068] Example 3: As Figure 11 shown, the process of catalyzing the synthesis of 2-acetonaphthone from 1-(2-naphthyl)ethanol is as follows:

[0069] 35.2 mg of 1-(2-naphthyl)ethanol, 8.7 mg of dimanganese decacarbonyl, and 5.1 mg of p-methylbenzenethiol were placed in a 25 mL reaction tube. After displacing nitrogen three times, 2 mL of N,N-dimethylformamide was added as a solvent under a nitrogen stream, and then 4.6 mg of triethylsilane was added. The bottle stopper was tightened, the reaction temperature was raised to 60 °C, and after reacting for 36 h, the solvent was removed. The white solid 2-acetonaphthone was obtained by column chromatography separation, and the nuclear magnetic resonance data was 1 1H NMR (400 MHz, Chloroform-d) δ 8.50 - 8.39 (m, 1H), 8.03 (dd, J = 8.7, 1.8 Hz, 1H), 7.96 (dd, J = 8.0, 1.4 Hz, 1H), 7.88 (dd, J = 8.4, 5.5 Hz, 2H), 7.58 (dddd, J = 19.4, 8.2, 6.9, 1.4 Hz, 2H), 2.72 (s, 3H). 1313C NMR (126 MHz, Chloroform-d) δ 198.15, 135.61, 134.50, 132.53, 130.23, 129.57, 128.50, 128.44, 127.81, 126.80, 123.91, 26.72. The nuclear magnetic resonance spectrum is as shown in Figure 12 and Figure 13 shown, where the mass of the finally obtained 2-acetonaphthone is 27.9 mg and the yield is 82%.

[0070] Example 4: As shown in Figure 14 shown, the process for catalyzing the synthesis of 3-chlorobenzophenone from 3-chlorodiphenylmethanol is as follows:

[0071] 43.7 mg of 3-chlorodiphenylmethanol, 8.8 mg of decacarbonyldimanganese, and 5.2 mg of p-methylthiophenol were placed in a 25 mL reaction tube. After displacing nitrogen three times, 2 mL of N,N-dimethylformamide was added as a solvent under a nitrogen stream, and then 4.6 mg of triethylsilane was added. The bottle stopper was tightened, the reaction temperature was raised to 80 °C, and after reacting for 48 h, the solvent was removed. The yellow solid 3-chlorobenzophenone was obtained by column chromatography. The nuclear magnetic data are 1 1H NMR (400 MHz, Chloroform-d) δ 7.81 - 7.73 (m, 4H), 7.63 - 7.58 (m, 1H), 7.48 (dd, J = 14.7, 8.1 Hz, 4H). 13 13C NMR (126 MHz, Chloroform-d) δ 195.68, 139.05, 137.38, 136.01, 132.80, 131.61, 130.08, 128.79, 128.55. The nuclear magnetic resonance spectrum is as shown in Figure 15 and Figure 16 shown, where the mass of the finally obtained 3-chlorobenzophenone is 30.6 mg and the yield is 71%.

[0072] Example 5: As shown in Figure 17 shown, the process for catalyzing the synthesis of phenylcyclopropyl ketone from α-cyclopropylbenzyl alcohol is as follows:

[0073] 29.3 mg of α-cyclopropylbenzyl alcohol, 8.7 mg of decacarbonyldimanganese, and 5.2 mg of p-methylthiophenol were placed in a 25 mL reaction tube. After displacing nitrogen three times, 2 mL of N,N-dimethylformamide was added as a solvent under a nitrogen stream, and then 4.5 mg of triethylsilane was added. The bottle stopper was tightened, the reaction temperature was raised to 80 °C, and after reacting for 36 h, the solvent was removed. The yellow solid phenylcyclopropyl ketone was obtained by column chromatography. The nuclear magnetic resonance data are 11H NMR (400 MHz, Chloroform-d) δ 8.05 - 7.96 (m, 2H), 7.59 - 7.53 (m, 1H), 7.48 (dd, J = 8.2, 6.8 Hz, 2H), 2.68 (tt, J = 7.8, 4.5 Hz, 1H), 1.27 - 1.22 (m, 2H), 1.05 (dq, J = 7.3, 3.6 Hz, 2H). 13 13C NMR (101 MHz, Chloroform-d) δ 200.82, 138.13, 132.85, 128.63, 128.14, 17.27, 11.80, and the nuclear magnetic resonance spectra are as Figure 18 and Figure 19 shown, where the mass of the finally obtained phenylcyclopropyl ketone is 21.9 mg and the yield is 75%.

[0074] Those of ordinary skill in the art should understand that the discussion of any of the above embodiments is merely exemplary and is not intended to imply that the scope of the present invention is limited to these examples; under the concept of the present invention, the technical features in the above embodiments or different embodiments can also be combined, the steps can be implemented in any order, and there are many other variations in different aspects of the present invention as described above, which are not provided in detail for the sake of brevity.

[0075] The present invention is intended to cover all such substitutions, modifications, and variations that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for dehydrogenating alcohols catalyzed by manganese carbonyl, characterized in that, A synthesis method of aldehyde compounds and a synthesis method of ketone compounds; The synthesis method of the aldehyde compounds is as follows: Add decacarbonyldimanganese, a hydrogen positive donor and a hydrogen negative donor to a primary alcohol substrate, react in an organic solvent under an inert gas atmosphere at 60 - 80 °C for 24 - 48 h, and the aldehyde compounds can be obtained after column chromatography separation; The synthesis method of the ketone compounds is as follows: Add decacarbonyldimanganese, a hydrogen positive donor and a hydrogen negative donor to a secondary alcohol substrate, react in an organic solvent under an inert gas atmosphere at 60 - 80 °C for 24 - 48 h, and the ketone compounds can be obtained after column chromatography separation.

2. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 1, characterized in that The structural formula of the primary alcohol substrate is as follows: Wherein the R1 group is an aryl group; the R2 group is a hydrogen atom.

3. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 2, characterized in that, The primary alcohol is m-nitrobenzyl alcohol and p-methoxybenzyl alcohol.

4. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 1, characterized in that, The structural formula of the secondary alcohol is as follows: Wherein the R1 group is an aryl group; the R2 group is any one of an aryl group and an alkyl group.

5. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 4, wherein The secondary alcohol is any one of 1-(2-naphthyl)ethanol, 3-chlorodiphenylmethanol, and α-cyclopropylbenzyl alcohol.

6. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 1, wherein The hydrogen positive donor is any one of p-chlorothiophenol, p-nitrothiophenol, and p-methylthiophenol; The molar percentage of the hydrogen positive donor and benzyl alcohol is 15% - 35%.

7. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 1, characterized in that, The hydrogen negative donor is any one of triethylsilane and triisopropylsilane; 8. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 1, wherein, The molar percentage of the hydrogen negative donor and benzyl alcohol is 15% - 35%.

9. The method for dehydrogenating alcohol by catalyzing with manganese carbonyl according to claim 1, characterized in that, The molar percentage of decacarbonyldimanganese and benzyl alcohol is 5% - 15%.

10. The method for dehydrogenating alcohol catalyzed by manganese carbonyl according to claim 1, characterized in that, The organic solvent is any one of tetrahydrofuran, acetonitrile, toluene, and N,N-dimethylformamide; the inert gas includes but is not limited to nitrogen.

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