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CN118221511A - NNP-Mn catalyst, preparation method and method for synthesizing alpha-alkyl ketone - Google Patents

NNP-Mn catalyst, preparation method and method for synthesizing alpha-alkyl ketone Download PDF

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CN118221511A
CN118221511A CN202410220244.4A CN202410220244A CN118221511A CN 118221511 A CN118221511 A CN 118221511A CN 202410220244 A CN202410220244 A CN 202410220244A CN 118221511 A CN118221511 A CN 118221511A
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catalyst
nnp
reaction
ketone
alpha
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宋沛东
毛明珍
戎豪杰
孟庭庭
陈涛
徐泽刚
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Xian Modern Chemistry Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
    • C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/46—Oxygen atoms
    • C07D213/50—Ketonic radicals
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    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • C—CHEMISTRY; METALLURGY
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04—One of the condensed rings being a six-membered aromatic ring
    • C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline

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Abstract

The invention provides an NNP-Mn catalyst, a preparation method and a method for synthesizing alpha-alkyl ketone, wherein the NNP-Mn catalyst is a nitrogen phosphine tridentate ligand manganese catalyst. The preparation method of the NNP-Mn catalyst comprises three steps of preparing diphenyl phosphino-acetaldehyde hydrobromide dimer, preparing nitrogen phosphine ligand and preparing NNP-Mn catalyst. The method for synthesizing the alpha-alkyl ketone adopts NNP-Mn catalyst to catalyze alcohol compounds and ketone compounds to carry out alpha-alkylation reaction to generate alpha-alkyl ketone compounds. The invention takes alcohol as alkylating reagent, realizes alpha-alkylation reaction of alcohol and ketone by NNP-Mn catalyst, and prepares alpha-alkyl ketone compound with important synthesis value. The method is suitable for coupling substrates such as alkyl ketone, aryl ketone, heterocyclic aryl ketone, alkyl alcohol, benzyl alcohol, aryl alcohol and the like, and has wide substrate applicability.

Description

NNP-Mn catalyst, preparation method and method for synthesizing alpha-alkyl ketone
Technical Field
The invention belongs to the technical field of organic synthesis, relates to a manganese catalyst for hydrogen transfer reaction, and in particular relates to an NNP-Mn catalyst, a preparation method and a method for synthesizing alpha-alkyl ketone.
Background
The alpha-alkylation reaction of carbonyl compounds is an important method for constructing carbon-carbon bonds in synthetic chemistry, and one existing method for alpha-alkylation reaction is as follows: alcohol is used as an alkylating reagent to be dehydrogenated under the catalysis of transition metal to generate a ketone intermediate, the intermediate and a carbonyl compound are subjected to aldol condensation, and then hydrogen atom transfer is carried out to realize carbonyl alpha-alkylation reaction. The alpha-alkylation reaction of the above alkyl alcohols and carbonyl compounds catalyzed by noble metals (ruthenium, rhodium, iridium, palladium, etc.) has evolved over the past few years, however, relatively few reports of catalyzing the reaction by inexpensive metals (iron, manganese, copper, nickel, etc.).
The current report of success in the manganese catalyzed alcohol and ketone α -alkylation reactions is as follows: in 2018, maji et al realized similar ketone alpha-alkylation reaction at 140 ℃ by using a manganese catalyst generated in situ by pyridine-imine tridentate ligand and pentacarbonyl manganese bromide and potassium tert-butoxide, the reaction temperature of the catalytic system is higher, and the catalytic system has better reactivity only to benzophenones substrates, and the application range of the substrates is narrow. In 2019, ke Zhuofeng, subject group et al, achieved similar alpha-alkylation reactions using an azacyclo-carbene-manganese catalyst and sodium hydroxide at 110 ℃, and the catalytic system was poorly applicable to heterocyclic substrates. In 2016, the Beller group reported for the first time that manganese catalyzes the α -alkylation of alcohols and ketones using 2, 2-diisopropylphosphinodiethylamine ligand coordinated manganese catalyst, cesium carbonate as a base, producing a series of α -alkyl ketone compounds in moderate to excellent yields at 140 ℃, which catalysts are sensitive to water oxygen and require manipulation in a glove box. In 2019, sortais and EI-Sepelgy et al reported in succession that PNP-Mn catalyzed alpha-methylation of ketone and methanol, the catalyst amount was 2-3 mol%, sodium tert-butoxide and cesium carbonate were used as base (0.5-2 equivalent), methanol was used as methylating agent and solvent, a series of alpha-methyl ketone was synthesized under 85-120 ℃, the catalyst system needed to use equivalent base, the base amount was excessive, and the compatibility of functional group was poor.
From the above reports, the main drawbacks of the prior art are: the application range of the substrate for catalyzing alcohol and ketone to carry out alpha-alkylation reaction is narrow; the catalyst is sensitive to water and oxygen, so that the reaction condition is more severe, and the reaction is carried out in a nitrogen atmosphere at high temperature; the catalyst system needs to use equivalent alkali and the alkali consumption is larger.
Disclosure of Invention
Aiming at the defects and shortcomings in the prior art, the invention aims to provide an NNP-Mn catalyst, a preparation method and a method for synthesizing alpha-alkyl ketone, which solve the technical problem of poor substrate applicability when alcohol and ketone are used as raw materials for alpha-alkylation reaction in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
A method for synthesizing alpha-alkyl ketone adopts NNP-Mn catalyst to catalyze alcohol compound and ketone compound to make alpha-alkylation reaction so as to produce alpha-alkyl ketone compound.
The NNP-Mn catalyst has a chemical structural formula shown in a formula I:
the chemical structural formula of the ketone compound is shown as a formula II:
wherein:
R 1 is phenyl, substituted phenyl, 1-naphthyl, pyridine, furan, thiophene, cyclohexyl.
R 2 is hydrogen, methyl, ethyl, benzyl.
The chemical structural formula of the alcohol compound is shown as formula III:
wherein:
R 3 is alkyl group having 1 to 8 carbon atoms, phenyl group having 1 to 8 carbon atoms, substituted phenyl group having 1 to 8 carbon atoms, naphthyl group having 1 to 8 carbon atoms, benzyl group having 1 to 8 carbon atoms, substituted benzyl group having 1 to 8 carbon atoms.
The chemical structural formula of the alpha-alkyl ketone compound is shown as formula IV:
the invention also has the following technical characteristics:
Specifically, the alcohol compounds are benzyl alcohol, 2-thiophene methanol, 4-bromobenzyl alcohol and n-hexanol; the ketone compounds are acetophenone, 4-methoxyacetophenone, 1-tetralone and 3-acetyl pyridine; the alpha-alkyl ketone compounds are 1, 3-diphenyl-1-acetone, 1-phenyl-3-thiophene-2-yl propyl-1-ketone, 3- (4-bromophenyl) -1-phenyl-1-acetone, 1-phenyl-1-octanone, 1- (4-methoxyphenyl) -3-phenylpropyl-1-ketone, 2-benzyl-3, 4-dihydronaphthalene-1 (2H) -ketone and 3-phenyl-1- (3-pyridyl) -1-acetone.
Specifically, the conditions of the alpha-alkylation reaction are as follows: in a reaction system containing alkali and toluene, the reaction is carried out for 2 to 6 hours at the temperature of 90 to 130 ℃.
Specifically, the molar ratio of the ketone compound to the alcohol compound to the NNP-Mn catalyst to the alkali is 1:1-1.8:0.01-0.05:0.02-0.1.
The invention also protects an NNP-Mn catalyst, and the chemical structural formula of the NNP-Mn catalyst is shown as formula I:
The invention also provides a preparation method of the NNP-Mn catalyst, which comprises the following steps: firstly, preparing diphenyl phosphino-acetaldehyde hydrobromide dimer by taking 2-bromoacetaldehyde diethyl acetal and diphenyl potassium phosphate as reaction raw materials under the action of hydrobromic acid; then taking diphenylphosphino-acetaldehyde hydrobromide dimer and 8-aminoquinoline as reaction raw materials, and preparing a nitrogen-phosphine ligand under the action of sodium triacetoxyborohydride; finally, taking the nitrogen-phosphine ligand and the pentacarbonyl manganese bromide as raw materials to synthesize the NNP-Mn catalyst.
Specifically, the method comprises the following steps:
Step one, preparing diphenylphosphino-acetaldehyde hydrobromide dimer:
Dissolving diphenyl potassium phosphate in tetrahydrofuran to prepare an organic phosphorus salt solution; adding an organic phosphorus salt solution into a reaction container, then dropwise adding 2-bromoacetaldehyde diethyl acetal under stirring at the temperature of minus 30 ℃ to minus 20 ℃, adding hydrobromic acid aqueous solution after the dropwise adding, and stirring at the temperature of 30 ℃ to 50 ℃ for reaction for 8 to 12 hours; after the reaction liquid is cooled, firstly distilling off half of the solvent, then carrying out suction filtration to obtain a filter cake, and leaching, pumping the solvent and drying the filter cake to obtain the diphenylphosphino-acetaldehyde hydrobromide dimer.
Step two, preparing a nitrogen-phosphine ligand:
Adding the diphenylphosphino-acetaldehyde hydrobromide dimer, 8-aminoquinoline, sodium triacetoxyborohydride and tetrahydrofuran prepared in the step one into a reaction vessel, and stirring and reacting for 8-16 hours at the temperature of 20-30 ℃ in a nitrogen protection atmosphere; after the reaction is finished, adding a saturated ammonium chloride aqueous solution into the reaction solution to quench the reaction; and extracting the product by using ethyl acetate, back-extracting an organic phase obtained by extraction by using saturated saline, and finally sequentially drying, concentrating the organic phase and purifying by column chromatography to obtain the nitrogen-phosphine ligand.
Step three, preparing NNP-Mn catalyst:
adding the nitrogen-phosphine ligand, manganese pentacarbonyl bromide and tetrahydrofuran prepared in the second step into a reaction vessel, and stirring and reacting for 8-12 hours at the temperature of 70-90 ℃ in a nitrogen protection atmosphere; after the reaction is finished, carrying out suction filtration on the reaction liquid under the protection of nitrogen to obtain a filter cake, and leaching and drying the filter cake to obtain the NNP-Mn catalyst.
Specifically, in the first step, the molar weight ratio of the 2-bromoacetaldehyde diethyl acetal, the diphenyl phosphorus potassium and the hydrobromic acid is 1:1-2:1.5-3.
Specifically, in the second step, the molar ratio of the diphenylphosphino-acetaldehyde hydrobromide dimer, 8-aminoquinoline and sodium triacetoxyborohydride is 1:1-2:2-4.
Specifically, in the third step, the molar ratio of the nitrogen-phosphine ligand to the pentacarbonyl manganese bromide is (1-1.5): 1.
Compared with the prior art, the invention has the beneficial technical effects that:
According to the method for synthesizing the alpha-alkyl ketone, disclosed by the invention, the alpha-alkylation reaction of the alcohol and the ketone is realized by taking the alcohol as an alkylating reagent through an NNP-Mn catalyst, so that the alpha-alkyl ketone compound with important synthesis value is prepared. The method is suitable for coupling substrates such as alkyl ketone, aryl ketone, heterocyclic aryl ketone, alkyl alcohol, benzyl alcohol, aryl alcohol and the like, and has wide substrate applicability.
(II) the method for synthesizing alpha-alkyl ketone of the invention does not need protective atmosphere and high temperature conditions, namely, the reaction conditions are tolerant. In addition, the method uses a catalytic amount of manganese catalyst and a base, i.e., a lower amount of strong base.
(III) the NNP-Mn catalyst has stronger structural rigidity and coordination capacity, and can be stably stored in air; the catalyst has high catalytic activity in alpha-alkylation reaction of alcohol and ketone, and has the advantages of good selectivity and high yield (the highest yield can reach 96 percent); in addition, the catalyst has small dosage and higher catalytic efficiency.
According to the preparation method of the NNP-Mn catalyst, 8-aminoquinoline is used as a ligand framework, diphenyl phosphine structural units are introduced through reductive amination reaction to synthesize a nitrogen phosphine tridentate ligand, and then the nitrogen phosphine tridentate ligand and pentacarbonyl manganese bromide are complexed to prepare the novel manganese catalyst NNP-Mn.
The technical scheme of the invention is further described below by referring to examples.
Detailed Description
According to the preparation method of the NNP-Mn catalyst, 8-aminoquinoline is used as a ligand framework, diphenyl phosphine structural units are introduced through reductive amination reaction to synthesize a nitrogen phosphine tridentate ligand, and then the nitrogen phosphine tridentate ligand and pentacarbonyl manganese bromide are complexed to prepare the novel manganese catalyst NNP-Mn; the synthetic route is as follows:
Wherein:
Represents 2-bromoacetaldehyde diethyl acetal.
Represents potassium diphenylphosphate.
HBr represents hydrobromic acid.
Represents diphenylphosphino-acetaldehyde hydrobromide dimer. /(I)Represents 8-aminoquinoline.
Represents sodium triacetoxyborohydride.
Represents a nitrogen phosphine ligand.
Mn (CO) 5 Br represents manganese pentacarbonyl bromide.
Represents NNP-Mn catalyst.
The invention adopts NNP-Mn catalyst to catalyze the reaction process of alcohol and ketone alpha-alkylation as follows:
Wherein:
R 1 is phenyl, substituted phenyl, 1-naphthyl, pyridine, furan, thiophene, cyclohexyl.
R 2 is hydrogen, methyl, ethyl, benzyl.
R 3 is alkyl group having 1 to 8 carbon atoms, phenyl group having 1 to 8 carbon atoms, substituted phenyl group having 1 to 8 carbon atoms, naphthyl group having 1 to 8 carbon atoms, benzyl group having 1 to 8 carbon atoms, substituted benzyl group having 1 to 8 carbon atoms.
All materials and reagents used in the present invention are those known in the art unless specifically stated otherwise.
The following specific embodiments of the present application are given according to the above technical solutions, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical solutions of the present application fall within the protection scope of the present application.
Example 1:
The embodiment provides a preparation method of an NNP-Mn catalyst, which specifically comprises the following steps:
Step one, preparing diphenylphosphino-acetaldehyde hydrobromide dimer:
Dissolving diphenyl potassium phosphate in tetrahydrofuran to prepare an organic phosphorus salt solution (0.5M); to a dry three-necked flask equipped with a constant pressure dropping funnel and thermometer, 68mL of an organic phosphorus salt solution was added, then 6.8g of 2-bromoacetaldehyde diethyl acetal was added dropwise with stirring at-20℃and the system was naturally returned to room temperature after the addition, then 17.6mL of 10wt.% hydrobromic acid aqueous solution was added, and stirring was carried out at 40℃for 10 hours. After the reaction solution is cooled to room temperature, half of the solvent is distilled off, suction filtration is carried out, a filter cake is sequentially leached by 15mL of water and 15mL of ethyl acetate, the solvent is pumped down, and 19.3g of white solid product is obtained after vacuum drying, and the white solid product is diphenylphosphino-acetaldehyde hydrobromide dimer.
Step two, preparing a nitrogen-phosphine ligand:
To a dry round bottom flask, 1.24g of the diphenylphosphino-acetaldehyde hydrobromide dimer obtained in step one, 576mg of 8-aminoquinoline, 1.7g of sodium triacetoxyborohydride and 20mL of tetrahydrofuran were added and stirred at room temperature (20-30 ℃) for 12 hours under nitrogen protection; then 15mL of saturated ammonium chloride aqueous solution is added into the reaction liquid under the protection of nitrogen to quench the reaction, stirring is carried out for 10 minutes, 30mL of ethyl acetate is added for extraction, the organic phase is back extracted by 30mL of saturated saline solution, anhydrous sodium sulfate is dried for 30 minutes, the organic phase is concentrated, finally, the organic phase is subjected to rapid column chromatography purification under the inert gas atmosphere, and 1.17g of colorless liquid product is obtained, and the colorless liquid product is the nitrogen-phosphine ligand.
Step three, preparing NNP-Mn catalyst:
adding 800mg of the nitrogen-phosphine ligand prepared in the second step, 617mg of manganese pentacarbonyl bromide and 5mL of tetrahydrofuran into a dried Schlenk tube, and heating and stirring at 80 ℃ for 10 hours under the protection of nitrogen; the reaction solution is subjected to suction filtration under the protection of nitrogen, 5mL of methyl tertiary butyl ether and 5mL of n-hexane are sequentially used for leaching filter cakes, then the obtained solid is rapidly transferred into a round bottom flask, and after vacuum drying, 1g of pale yellow solid product is prepared.
In this example, the final pale yellow solid product obtained was identified and characterized as follows:
1H NMR(500MHz,DMSO-d6)：δppm 9.51(s,1H),8.51(dd,2H),8.21(d,1H),8.04(d,1H),7.82(t,3H),7.56(d,3H),7.42－7.23(m,2H),7.16(t,2H),6.88(t,2H),4.17－4.05(m,1H),3.21－3.06(m,2H),1.74－1.47(m,1H);
13C NMR(125MHz,DMSO-d6)：δppm 156.46,146.05,142.50,139.10,132.37,132.29,131.87,131.31,131.01,130.88,130.81,130.02,129.83,129.77,129.47,129.39,129.17,128.50,128.08,124.41,57.02,56.92;
31P NMR(202MHz，DMSO-d6)：δppm 68.31。
From the above structural characterization data, the pale yellow solid product prepared in this example was NNP-Mn catalyst. In this example, the NNP-Mn catalyst was produced in an yield of 82% and a content of 96%.
Example 2:
This example shows a method for catalyzing the alpha-alkylation of benzyl alcohol and acetophenone using the NNP-Mn catalyst prepared in example 1 as the catalyst; the method specifically comprises the following steps:
to a dry 15mL Schlenk tube, 60mg acetophenone, 65mg benzyl alcohol, 5.5mg NNP-Mn catalyst prepared in example 1, 2.2mg potassium tert-butoxide, and 1mL toluene were added, and heated at 110deg.C for 2 hours under stirring; cooling the system to room temperature, and adding 10mL of water to quench the reaction; then 10mL ethyl acetate is adopted to extract the product, and the organic phase is back extracted by saturated saline; drying the organic phase with anhydrous sodium sulfate for 30 minutes, and concentrating the organic phase; after purification by column chromatography, 96mg of a white solid product was obtained.
In this example, the final white solid product was identified and characterized as follows:
1H NMR(400MHz,CDCl3)δ7.93(d,2H),7.56(t,1H),7.46(t,2H),7.34-7.26(m,4H),7.22(t,1H),3.48-3.25(m,2H),3.15-2.96(m,2H).
13C NMR(100MHz,CDCl3)δ199.90,141.24,136.80,133.02,128.56,128.48,128.38,127.99,126.09,40.41,30.09.
from the above structural characterization data, the white solid prepared in this example was 1, 3-diphenyl-1-propanone. In this example, the yield of 1, 3-diphenyl-1-propanone was 91%.
The reaction route of this example is as follows:
Wherein:
KO t Bu represents potassium tert-butoxide.
NNP-Mn means NNP-Mn catalyst.
Indicating acetophenone.
Represents benzyl alcohol.
Represents 1, 3-diphenyl-1-propanone (CAS code 1083-30-3).
Example 3:
This example shows a method for catalyzing the alpha-alkylation reaction of 2-thiophenecanol and acetophenone using the NNP-Mn catalyst prepared in example 1 as the catalyst; the process is essentially the same as in example 2, except that: 69mg of 2-thiophenecanol was used in place of benzyl alcohol.
In this example, 89mg of a white solid product was finally obtained, which was identified and characterized as follows:
1H NMR(400MHz,CDCl3)δ7.91(d,2H),7.57(t,1H),7.47(t,2H),7.13(dd,1H),6.93(dd,1H),6.87(dd,1H),3.40-3.34(m,2H),3.33-3.27(m,2H).
13C NMR(100MHz,CDCl3)δ197.65,143.84,136.69,133.13,128.60,127.99,126.81,124.64,123.34,40.51,24.18.
From the above structural characterization data, the white solid product prepared in this example was 1-phenyl-3-thiophen-2-ylpropan-1-one. In this example, the yield of 1-phenyl-3-thiophen-2-ylpropan-1-one was 82%.
The reaction route of this example is as follows:
Wherein:
Represents 2-thiophenecanol.
Represents 1-Phenyl-3-thiophen-2-ylpropan-1-one (1-Phenyl-3-thiophen-2-ylpropan-1-one).
Example 4:
this example shows a method for catalyzing the alpha-alkylation reaction of 4-bromobenzyl alcohol and acetophenone using the NNP-Mn catalyst prepared in example 1 as the catalyst; the process is essentially the same as in example 2, except that: 112mg of 4-bromobenzyl alcohol was used instead of benzyl alcohol.
In this example, 127mg of a white solid product was finally obtained, which was identified and characterized as follows:
1H NMR(400MHz,CDCl3)δ7.94(d,2H),7.56(t,1H),7.50-7.37(m,4H),7.17-7.05(m,2H),3.28(t,2H),3.03(t,2H).
13C NMR(100MHz,CDCl3)δ197.97,140.21,136.68,133.13,131.50,130.19,128.60,127.96,119.83,40.01,29.38.
From the above structural characterization data, the white solid product produced in this example was 3- (4-bromophenyl) -1-phenyl-1-propanone. In this example, the yield of 3- (4-bromophenyl) -1-phenyl-1-propanone was 88%.
The reaction route of this example is as follows:
Wherein:
Represents 4-bromobenzyl alcohol.
Represents 3- (4-bromophenyl) -1-phenyl-1-propanone (CAS code 52168-41-9).
Example 5:
This example shows a method of catalyzing the α -alkylation of n-hexanol and acetophenone using the NNP-Mn catalyst prepared in example 1 as the catalyst; the process is essentially the same as in example 2, except that: 61mg of n-hexanol was used instead of benzyl alcohol.
In this example, 87mg of a white solid product was finally obtained, which was identified and characterized as follows:
1H NMR(400MHz,CDCl3)δ7.92(d,2H),7.55(t,1H),7.46(t,2H),2.96(t,2H),1.91-1.67(m,2H),1.43-1.15(m,8H),0.88(t,3H).
13C NMR(100MHz,CDCl3)δ201.83,137.10,132.83,128.52,128.04,38.63,31.70,29.33,29.13,24.39,22.61,14.06.
From the above structural characterization data, the white solid product prepared in this example was 1-phenyl-1-octanone. In this example, the yield of 1-phenyl-1-octanone was 85%.
The reaction route of this example is as follows:
Wherein:
Represents n-hexanol.
Represents 1-phenyl-1-octanone (CAS code 1674-37-9).
Example 6:
This example shows a method for catalyzing the alpha-alkylation reaction of benzyl alcohol and 4-methoxyacetophenone using the NNP-Mn catalyst prepared in example 1 as the catalyst; the process is essentially the same as in example 2, except that: 75mg of 4-methoxyacetophenone was used instead of acetophenone.
In this example, 115mg of a white solid product was finally obtained, which was identified and characterized as follows:
1H NMR(400MHz,CDCl3)δ7.92(d,2H),7.38-7.14(m,5H),6.92(d,2H),3.86(s,3H),3.25(t,2H),3.18-2.94(m,2H).
13C NMR(100MHz,CDCl3)δ198.13,163.42,141.43,130.28,129.93,128.48,128.40,126.05,113.70,55.44,40.10,30.31.
from the above structural characterization data, the white solid product obtained in this example was 1- (4-methoxyphenyl) -3-phenylpropan-1-one. In this example, the yield of 1- (4-methoxyphenyl) -3-phenylpropan-1-one was 96%.
The reaction route of this example is as follows:
Wherein:
represents 4-methoxyacetophenone.
Represents 1- (4-methoxyphenyl) -3-phenylpropan-1-one (CAS code 5739-38-8).
Example 7:
This example shows a method for catalyzing the alpha-alkylation reaction of benzyl alcohol and 1-tetralone using the NNP-Mn catalyst prepared in example 1 as the catalyst; the process is essentially the same as in example 2, except that: 73mg of 1-tetralone was used instead of acetophenone.
In this example, 106mg of a white solid product was finally obtained. The white solid product was identified and characterized as follows:
1H NMR(400MHz,CDCl3)δ8.12(dd,1H),7.47(td,1H),7.36-7.28(m,3H),7.28-7.18(m,4H),3.50(dd,1H),3.03-2.85(m,2H),2.81-2.71(m,1H),2.65(dd,1H),2.12(dq,1H),1.80(m,1H).
13C NMR(100MHz,CDCl3)δ199.27,144.00,140.00,133.24,132.43,129.23,128.68,128.37,127.51,126.59,126.10,49.42,35.64,28.59,27.63.
From the above structural characterization data, the white solid product prepared in this example was 2-benzyl-3, 4-dihydronaphthalen-1 (2H) -one. In this example, the yield of 2-benzyl-3, 4-dihydronaphthalen-1 (2H) -one was 90%.
The reaction route of this example is as follows:
Wherein:
represents 1-tetralone.
Represents 2-benzyl-3, 4-dihydronaphthalen-1 (2H) -one (CAS code 27019-08-5). /(I)
Example 8:
This example shows a method for catalyzing the alpha-alkylation reaction of benzyl alcohol and 3-acetylpyridine using the NNP-Mn catalyst prepared in example 1 as the catalyst; the process is essentially the same as in example 2, except that: 61mg of 3-acetylpyridine was used instead of acetophenone.
In this example, 84mg of a white solid product was finally obtained, which was identified and characterized as follows:
1H NMR(400MHz,CDCl3)δ9.12(s,1H),8.77(d,1H),8.22(dt,1H),7.41(dd,1H),7.31-7.20(m,5H),3.32(t,2H),3.09(t,2H).
13C NMR(100MHz,CDCl3)δ198.16,153.44,149.55,140.72,135.32,132.05,128.58,128.38,126.29,123.63,40.67,29.79.
from the above structural characterization data, the white solid product produced in this example was 3-phenyl-1- (3-pyridyl) -1-propanone. In this example, the yield of 3-phenyl-1- (3-pyridyl) -1-propanone was 80%.
The reaction route of this example is as follows:
Wherein:
Represents 3-acetylpyridine.
Represents 3-phenyl-1- (3-pyridyl) -1-propanone (CAS code 1802-36-4). /(I)

Claims (10)

1. A method for synthesizing alpha-alkyl ketone is characterized in that NNP-Mn catalyst is adopted to catalyze alcohol compounds and ketone compounds to carry out alpha-alkylation reaction to generate alpha-alkyl ketone compounds;
The NNP-Mn catalyst has a chemical structural formula shown in a formula I:
the chemical structural formula of the ketone compound is shown as a formula II:
wherein:
R 1 is phenyl, substituted phenyl, 1-naphthyl, pyridine, furan, thiophene, cyclohexyl;
R 2 is hydrogen, methyl, ethyl, benzyl;
the chemical structural formula of the alcohol compound is shown as formula III:
wherein:
R 3 is alkyl with 1 to 8 carbon atoms, phenyl with 1 to 8 carbon atoms, substituted phenyl with 1 to 8 carbon atoms, naphthyl with 1 to 8 carbon atoms, benzyl with 1 to 8 carbon atoms, or substituted benzyl with 1 to 8 carbon atoms;
the chemical structural formula of the alpha-alkyl ketone compound is shown as formula IV:
2. The method for synthesizing alpha-alkyl ketone according to claim 1, wherein the alcohol compound is benzyl alcohol, 2-thiophenmethanol, 4-bromobenzyl alcohol and n-hexanol;
The ketone compounds are acetophenone, 4-methoxyacetophenone, 1-tetralone and 3-acetyl pyridine;
The alpha-alkyl ketone compounds are 1, 3-diphenyl-1-acetone, 1-phenyl-3-thiophene-2-yl propyl-1-ketone, 3- (4-bromophenyl) -1-phenyl-1-acetone, 1-phenyl-1-octanone, 1- (4-methoxyphenyl) -3-phenylpropyl-1-ketone, 2-benzyl-3, 4-dihydronaphthalene-1 (2H) -ketone and 3-phenyl-1- (3-pyridyl) -1-acetone.
3. The method for synthesizing an α -alkyl ketone according to claim 1, wherein the α -alkylation reaction conditions are: in a reaction system containing alkali and toluene, the reaction is carried out for 2 to 6 hours at the temperature of 90 to 130 ℃.
4. The method for synthesizing alpha-alkyl ketone according to claim 3, wherein the molar ratio of ketone compound, alcohol compound alcohol, NNP-Mn catalyst and alkali is 1:1-1.8:0.01-0.05:0.02-0.1.
5. The NNP-Mn catalyst is characterized in that the chemical structural formula of the NNP-Mn catalyst is shown as formula I:
6. A method of preparing the NNP-Mn catalyst of claim 5, comprising: firstly, preparing diphenyl phosphino-acetaldehyde hydrobromide dimer by taking 2-bromoacetaldehyde diethyl acetal and diphenyl potassium phosphate as reaction raw materials under the action of hydrobromic acid; then taking diphenylphosphino-acetaldehyde hydrobromide dimer and 8-aminoquinoline as reaction raw materials, and preparing a nitrogen-phosphine ligand under the action of sodium triacetoxyborohydride; finally, taking the nitrogen-phosphine ligand and the pentacarbonyl manganese bromide as raw materials to synthesize the NNP-Mn catalyst.
7. The method for preparing an NNP-Mn catalyst according to claim 6, wherein the method comprises the steps of:
Step one, preparing diphenylphosphino-acetaldehyde hydrobromide dimer:
Dissolving diphenyl potassium phosphate in tetrahydrofuran to prepare an organic phosphorus salt solution; adding an organic phosphorus salt solution into a reaction container, then dropwise adding 2-bromoacetaldehyde diethyl acetal under stirring at the temperature of minus 30 ℃ to minus 20 ℃, adding hydrobromic acid aqueous solution after the dropwise adding, and stirring at the temperature of 30 ℃ to 50 ℃ for reaction for 8 to 12 hours; after the reaction liquid is cooled, firstly distilling off half of the solvent, then carrying out suction filtration to obtain a filter cake, and leaching, pumping the solvent and drying the filter cake to obtain diphenylphosphino-acetaldehyde hydrobromide dimer;
Step two, preparing a nitrogen-phosphine ligand:
adding the diphenylphosphino-acetaldehyde hydrobromide dimer, 8-aminoquinoline, sodium triacetoxyborohydride and tetrahydrofuran prepared in the step one into a reaction vessel, and stirring and reacting for 8-16 hours at the temperature of 20-30 ℃ in a nitrogen protection atmosphere; after the reaction is finished, adding a saturated ammonium chloride aqueous solution into the reaction solution to quench the reaction; extracting a product by adopting ethyl acetate, back-extracting an organic phase obtained by extraction by adopting saturated saline water, and finally sequentially drying, concentrating the organic phase and purifying by column chromatography to obtain a nitrogen-phosphine ligand;
Step three, preparing NNP-Mn catalyst:
adding the nitrogen-phosphine ligand, manganese pentacarbonyl bromide and tetrahydrofuran prepared in the second step into a reaction vessel, and stirring and reacting for 8-12 hours at the temperature of 70-90 ℃ in a nitrogen protection atmosphere; after the reaction is finished, carrying out suction filtration on the reaction liquid under the protection of nitrogen to obtain a filter cake, and leaching and drying the filter cake to obtain the NNP-Mn catalyst.
8. The method for preparing an NNP-Mn catalyst according to claim 7, wherein in the first step, the molar ratio of the 2-bromoacetaldehyde diethyl acetal, the diphenyl phosphate potassium to the hydrobromic acid is 1:1-2:1.5-3.
9. The method for preparing NNP-Mn catalyst according to claim 7, wherein in the second step, the molar ratio of diphenylphosphino-acetaldehyde hydrobromide dimer, 8-aminoquinoline and sodium triacetoxyborohydride is 1:1-2:2-4.
10. The method for preparing NNP-Mn catalyst according to claim 7, wherein in step three, the molar ratio of the nitrogen-phosphine ligand to manganese pentacarbonyl bromide is (1 to 1.5): 1.
CN202410220244.4A 2024-02-28 2024-02-28 NNP-Mn catalyst, preparation method and method for synthesizing alpha-alkyl ketone Pending CN118221511A (en)

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