CN115093346A - Method for preparing nitrile compounds from different substituted cycloalkanones in one step - Google Patents
Method for preparing nitrile compounds from different substituted cycloalkanones in one step Download PDFInfo
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Abstract
A method for preparing nitrile compounds by different substituted cycloalkanones in one step is characterized in that substituted cycloalkanones are used as initial raw materials, green pollution-free air or oxygen is used as an oxidant, and under the induction of visible light, an ammoniation reagent, a cocatalyst, an oxidant and a photocatalyst are combined to realize the carbon-carbon bond cracking/cyaniding reaction of the 2-substituted cycloalkanones; the cheap metal salt catalytic reaction has mild conditions, does not need high temperature, high pressure and strong oxidation reagent, has simple operation process, simple post-treatment, small environmental pollution, cheap and easily obtained catalyst, low cost and small pollution, and has stronger application potential.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a method for preparing nitrile compounds from different substituted cycloalkanones in one step.
Background
Alkylnitriles are a special class of building blocks found in a variety of natural products and drug molecules. Cyano is one of the most useful functional groups in organic synthesis, is readily converted to other functional groups, and is widely used in the preparation of amines, amides, carboxylic acids, heterocycles and the like. In the last decades, the traditional methods for the synthesis of alkylnitriles have been: industrially, the cyanation product is mainly generated by the reaction of olefin and virulent hydrogen cyanide or a substrate capable of generating hydrogen cyanide, such as acetone cyanohydrin or trimethyl cyanosilicon, under the catalysis of transition metal such as Ni, Pd or Co, etc., however, the virulent cyanide limits the further development of the reaction; nucleophilic substitution reactions of aliphatic halocarbons or sulfonates with metal cyanides are predominantly employed in the laboratory, however the tendency for elimination reactions to occur in tertiary alkyl systems is very significant, limiting the utility of the reaction and the use of highly toxic cyanides is unavoidable.
Adiponitrile, which is one of the main raw materials of nylon 66, is often used as a plasticizer, an antioxidant, a stabilizer, a sterilizing agent, an extracting agent, a bleaching agent, a vulcanizing agent, etc. in the field of fine chemical engineering. The prior preparation methods of adiponitrile mainly comprise a butadiene direct hydrocyanation method, an acrylonitrile electrolysis method, a caprolactam method, adipic acid ammoniation dehydration, a butadiene carbonylation method and the like. However, the strategies also have the problems of great technical difficulty, requirement on a matched raw material hydrocyanic acid production device, higher requirements on primary investment and production scale and the like. Therefore, it is important to develop a mild and efficient alkyl nitrile synthesis reaction without the participation of highly toxic cyanide.
Due to the characteristics of abundant reserves, greenness, environmental protection and the like of visible light, visible light catalysis becomes a popular field of organic synthesis research. In the last decade, visible light-induced organic synthesis and photocatalytic free radical reaction have become the hot points of attention of chemists, and especially in the aspect of carbon-carbon bond activation, visible light catalysis provides an effective way for the rapid conversion of organic molecular frameworks more efficiently. For example, the scholars ' Shawen, the scholars ' Johning's scholars ' and the scholars ' report that a series of alkyl nitrile compounds containing carbonyl functional group are prepared by photocatalytic carbon-carbon bond cleavage/Kornblum type oxidation of cyclic ketoxime ester. However, the reaction requires derivatization of the cycloalkanone into oxime and then conversion of the oxime ester into oxime ester for reaction, which undoubtedly increases the synthesis steps, reduces the atom economy and synthesis efficiency of the reaction, and is not suitable for large-scale and industrial production. Therefore, the research of developing a simple, efficient and environment-friendly cyanation reaction by using cheap and easily available cycloalkanone as a substrate is especially necessary.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a method for preparing nitrile compounds by different substituted cycloalkanones in one step, which does not need to adopt highly toxic cyanide and takes the cycloalkanone as a raw material to prepare alkyl nitrile in one step.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a one-step process for the preparation of nitrile compounds from differently substituted cycloalkanones comprising the steps of:
(1) adopting a dry reaction tube, adding a stirrer, and adding a catalyst accounting for C mol% and a photosensitizer accounting for D mol% in the air or oxygen atmosphere; diluting A mmol of cycloalkanone and B mmol of ammoniation reagent with E mL of solvent to form a mixed solution, wherein A: B: E: 1 (1.5-2) and (5-15); c and D are 1 to 5 to 10 percent and 3 to 8 percent;
(2) carrying out reaction under the irradiation of a light source, and monitoring the reaction (2, 4-dinitrophenylhydrazine and potassium permanganate solution color development) by a TLC plate until the reaction is complete;
(3) and (3) distilling the reacted mixed solution under reduced pressure, evaporating to remove the solvent, and separating the crude product by column chromatography.
The ammoniation reagent is any one or combination of more than one of ammonia gas, ammonia water, urea, ammonium bicarbonate, ammonium carbonate, ammonium acetate, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium iodide, ammonium fluoride, ammonium bromide or ammonium chloride.
The catalyst comprises copper salt, ferric salt, zinc chloride, magnesium chloride, aluminum chloride, cerium chloride, Lewis acid, hydrochloric acid, sulfuric acid, acetic acid,
One or more of acids, wherein the cupric salt comprises copper trifluoromethanesulfonate, cuprous trifluoromethanesulfonate, cupric chloride, cuprous chloride, cupric bromide, cupric nitrate, cupric acetate, copper tetra-acetonitrile hexafluorophosphate and cupric oxide; the iron salt comprises iron triflate, ferrous triflate, iron acetylacetonate, ferrous acetylacetonate, ferric chloride, ferrous chloride, ferric bromide, iron acetate, ferric p-toluenesulfonate, cobalt acetate, cobalt nitrate, cobalt acetylacetonate, cobalt acetate, cobalt chloride, nickel fluoride, nickel bromide, nickel nitrate, nickel tetrafluoroborate, palladium acetylacetonate, palladium acetate, palladium trifluoroacetate, palladium/carbon, palladium chloride, or combinations thereof.
The photocatalyst is one or a combination of more of an iridium complex photosensitizer, a ruthenium complex photosensitizer, an organic photosensitizer and an organic dye;
wherein the iridium complex photosensitizer comprises [ Ir (dF (CF) 3 )ppy) 2 (dtbbpy)]PF 6 、 [Ir(ppy) 2 (dtbbpy)]PF 6 、[Ir(dF(CF 3 )ppy) 2 (5,5’-dCF 3 bpy)]PF 6 (ii) a Ruthenium complex photosensitizers include Ru (bpz) 3 (PF 6 ) 2 、Ru(bpm) 3 (PF 6 ) 2 、Ru(dtbppy) 3 (PF 6 ) 2 、Ru(phen) 3 Cl 2 The organic photosensitizer comprises triphenylpyrane salt, mesitylacridine salt, 4CzIPN, tetraphenylporphyrin and vitamin B 2 The organic dye includes rhodamine, methyl red, methylene blue, fluorescein, eosin Y, and rosolic acid.
The formula of the cycloalkanone is as follows:
the solvent is one or more of toluene, xylene, trifluorotoluene, acetonitrile, propionitrile, dichloroethane, chloroform, carbon tetrachloride, methyl tert-butyl ether, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, methanol, ethanol, tert-amyl alcohol and the like.
The light source is irradiated by visible light, including 460 and 470nm blue light, white light and sunlight.
The step (2) can also adopt a continuous flow mode for preparation, and specifically comprises the following steps: and (2) introducing the mixed solution obtained in the step (1) into a colorless transparent tube through a continuous flow chemical reactor, allowing the reaction solution to perform flow reaction in the transparent tube under the irradiation of visible light by the transparent tube at a flow rate of 5-20mL/min, and monitoring the reaction (2, 4-dinitrophenylhydrazine and potassium permanganate solution color development) through a TLC plate until the reaction is complete.
The flow rate of the continuous flow chemical reactor is 5-20 mL/min.
The advantages and the characteristics of the invention are as follows:
(1) substituted cycloalkanone is used as an initial raw material, green and pollution-free air (oxygen) is used as an oxidant, and an ammoniation reagent, a cocatalyst, the oxidant and a photocatalyst are combined to realize the carbon-carbon bond cracking/cyaniding reaction of the 2-substituted cycloalkanone under the induction of visible light; the cheap metal salt catalytic reaction has mild reaction conditions, does not need high temperature, high pressure and strong oxidation reagent, has simple operation process, simple post-treatment, small environmental pollution and cheap and easily obtained catalyst.
(2) The reaction adopts a continuous flow process, the dosage of reactants is enlarged, the reaction time is shortened, and the support is provided for subsequent commercial scale production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of adiponitrile.
FIG. 2 is a nuclear magnetic carbon spectrum of adiponitrile.
FIG. 3 is a nuclear magnetic hydrogen spectrum of 6-oxoheptanenitrile.
FIG. 4 is a nuclear magnetic carbon spectrum of 6-oxoheptanenitrile.
FIG. 5 is a nuclear magnetic hydrogen spectrum of 6-oxo-6-phenylhexanenitrile.
FIG. 6 is a nuclear magnetic carbon spectrum of 6-oxo-6-phenylhexanenitrile.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the following examples are set forth herein. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
Example one
The embodiment comprises the following steps:
to a 10mL Schlenk tube containing magnetons, ammonium acetate (2equiv), Cu (OTf) were added 2 (5 mol%) methyl red (2 mol%). Cyclohexanone (0.2mmol) was dissolved in 2mL of acetonitrile, and the mixture was added to the mixture under an air atmosphere. The reaction was carried out under irradiation with blue light (460-470nm,10W) and monitored by TLC plates. The reacted mixture was distilled under reduced pressure, the solvent was distilled off, column chromatography was performed using 200-300 mesh silica gel, and then ethyl acetate/petroleum ether (3:1) was used as an eluent to obtain adiponitrile (7.6mg, yield 35%) as an oily liquid.
The reaction equation is as follows:
the product structure is as follows:
referring to fig. 1 and 2, the hydrogen and carbon spectra data of the product are as follows:
1 H NMR(400MHz,CDCl 3 )δ1.57-1.71(m,4H),2.09(s,3H),2.31 (t,J＝6.6Hz,2H),2.45(t,J＝6.6Hz,2H). 13 C NMR(100MHz,CDCl 3 ) δ16.6,34.2,118.7.
example two
The embodiment comprises the following steps:
to a 10mL Schlenk tube containing magnetons, ammonium acetate (1.5equiv), Cu (OAc) were added 2 (5 mol%), Eosin Y (5 mol%). 2-Methylcyclohexanone (0.2mmol) was dissolved in 2mL of MTBE, and a mixture of 2-methylcyclohexanone and acetonitrile was added under an air atmosphere. The reaction was carried out under irradiation with blue light (460-470nm,10W) and monitored by TLC plates. Distilling the reacted mixture under reduced pressure, evaporating to remove the solvent, performing column chromatography separation by using 200-mesh and 300-mesh silica gel, and introducingEthyl peracetate/petroleum ether (3:1) as eluent gave 6-oxoheptanenitrile (14.3mg, 57% yield) as a colorless oil.
The reaction equation is as follows:
the structure of the product is as follows:
referring to fig. 3 and 4, the hydrogen and carbon spectra data of the product are as follows: 1 H NMR(400MHz,CDCl 3 )δ1.63-1.73(m,4H),2.14(s,3H),2.34(t,J ＝6.6Hz,2H),2.49(t,J＝6.6Hz,2H). 13 C NMR(100MHz,CDCl 3 )δ 17.1,22.6,24.8,29.9,42.4,119.4,207.7.
EXAMPLE III
The embodiment comprises the following steps:
adding ammonia (2equiv) and Fe (OTf) into a 10mL Schlenk tube filled with magnetons 2 (10mol％)，Ir(ppy) 3 (2 mol%). 2-Phenylcyclohexanone (0.2mmol) was dissolved in 2mL of DMAc and added under an air atmosphere. The reaction was carried out under irradiation with white light (400-760nm, 30W) and monitored by TLC plates. The reacted mixture was distilled under reduced pressure, the solvent was distilled off, column chromatography was performed using 200-mesh 300-mesh silica gel, and ethyl acetate/petroleum ether (3:1) was used as an eluent to obtain 6-oxo-6-phenylhexanenitrile (18.3mg, 49% yield) as a white solid.
The reaction equation is as follows:
the product structure is as follows:
referring to fig. 5 and 6, the hydrogen and carbon spectra data of the product are as follows: 1 H NMR(400MHz,CDCl 3 ):δ7.96–7.93(m,2H),7.59–7.55(m,1H), 7.48–7.45(m,2H),3.04(t,J＝7.2Hz,2H),2.40(t,J＝7.2Hz,2H), 1.94–1.87(m,2H),1.80–1.73(m,2H)； 13 C NMR(100MHz,CDCl 3 ):δ 199,136.6,133.2,128.6,127.9,119.5,37.3,24.9,23,17.1.
example four:
the embodiment comprises the following steps:
in a 100mL three-necked flask, FeBr was added 2 (10 mol%), vitamin B 2 (7 mol%). Cyclohexanone (5mmol) was dissolved in 2mL of CH 3 NO 2 To a three-necked flask, and then ammonia (15mmol) was dissolved in 2mL of CH 3 NO 2 Adding into a three-neck bottle, adding 46 mLCH 3 NO 2 . The reaction solution is introduced into a colorless transparent tube through a continuous flow chemical reactor, the reaction solution flows in the transparent tube under the irradiation of blue light (460-470nm,30W) until the reaction is completed, the flow rate is 10mL/min, and the reaction is monitored by a TLC plate. Distilling the reacted mixture under reduced pressure, evaporating to remove the solvent, performing column chromatography separation by using 200-mesh 300-mesh silica gel, and obtaining oily liquid adiponitrile (156.8mg, yield 29%) by using ethyl acetate/petroleum ether (3:1) as an eluent
The above description is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered as falling within the technical scope of the present invention, and the technical solution and the invention thereof should be substituted or changed by equivalent or modified within the technical scope of the present invention.
Claims (9)
1. A method for preparing nitrile compounds from different substituted cycloalkanones in one step, which is characterized by comprising the following steps:
(1) adopting a dry reaction tube, adding a stirrer, and adding a catalyst accounting for C mol% and a photosensitizer accounting for D mol% in the air or oxygen atmosphere; diluting A mmol of cyclic alkanone and B mmol of ammoniation reagent with E mL of solvent to form a mixed solution, wherein A: B: E ═ 1, (1.5-2): 5-15; c, D is 1 to 5 to 10 percent and 3 to 8 percent;
(2) carrying out reaction under the irradiation of a light source, and monitoring the reaction by a TLC plate until the reaction is complete;
(3) and (3) distilling the reacted mixed solution under reduced pressure, evaporating to remove the solvent, and separating the crude product by column chromatography.
2. The method for preparing nitrile compounds from different substituted cycloalkanones in one step according to claim 1, wherein the ammoniating agent is any one or a combination of any more than one of ammonia gas, ammonia water, urea, ammonium bicarbonate, ammonium carbonate, ammonium acetate, ammonium sulfate, ammonium bisulfate, ammonium nitrate, ammonium iodide, ammonium fluoride, ammonium bromide or ammonium chloride.
3. The method of claim 1, wherein the catalyst comprises copper salt, iron salt, zinc chloride, magnesium chloride, aluminum chloride, cerium chloride, Lewis acid, hydrochloric acid, sulfuric acid, acetic acid, sulfuric acid, or mixtures thereof,
One or more of acids, wherein the copper salt comprises copper trifluoromethanesulfonate, cuprous trifluoromethanesulfonate, cupric chloride, cuprous chloride, cupric bromide, cupric nitrate, cupric acetate, copper tetraacetonitrile hexafluorophosphate and cupric oxide; the iron salt comprises iron triflate, ferrous triflate, iron acetylacetonate, ferrous acetylacetonate, ferric chloride, ferrous chloride, ferric bromide, ferric acetate, ferric p-toluenesulfonate, cobalt acetate, cobalt nitrate, cobalt acetylacetonate, cobalt acetate, cobalt chloride, nickel fluoride, nickel bromide, nickel nitrate, nickel tetrafluoroborate, palladium acetylacetonate, palladium acetate, palladium trifluoroacetate, palladium/carbon, palladium chloride, or a combination thereof.
4. The method for preparing nitrile compounds from different substituted cycloalkanones in one step as claimed in claim 1, wherein the photocatalyst is one or more of iridium complex photosensitizer, ruthenium complex photosensitizer, organic photosensitizer and organic dye;
wherein the iridium complex photosensitizer comprises [ Ir (dF (CF) 3 )ppy) 2 (dtbbpy)]PF 6 、[Ir(ppy) 2 (dtbbpy)]PF 6 、[Ir(dF(CF 3 )ppy) 2 (5,5’-dCF 3 bpy)]PF 6 (ii) a Ruthenium complex photosensitizers include Ru (bpz) 3 (PF 6 ) 2 、Ru(bpm) 3 (PF 6 ) 2 、Ru(dtbppy) 3 (PF 6 ) 2 、Ru(phen) 3 Cl 2 The organic photosensitizer comprises triphenylpyrane salt, mesitylacridine salt, 4CzIPN, tetraphenylporphyrin and vitamin B 2 The organic dye includes rhodamine, methyl red, methylene blue, fluorescein, eosin Y, and rosolic acid.
5. A process according to claim 1 for the one-step preparation of nitrile compounds from different substituted cycloalkanones, wherein said cycloalkanone has the formula:
6. the method for preparing nitrile compounds from different substituted cycloalkanones in one step as claimed in claim 1, wherein the solvent is one or more of toluene, xylene, trifluorotoluene, acetonitrile, propionitrile, dichloroethane, chloroform, carbon tetrachloride, methyl tert-butyl ether, tetrahydrofuran, N-dimethylformamide, N-methylpyrrolidone, methanol, ethanol, tert-amyl alcohol, etc.
7. The method as claimed in claim 1, wherein the light source is visible light including 460-470nm blue light, white light and sunlight.
8. A method for preparing nitrile compounds from different substituted cycloalkanones in one step according to claim 1, wherein the step (2) is also performed by a continuous flow method, specifically: and (2) introducing the mixed solution obtained in the step (1) into a colorless transparent tube through a continuous flow chemical reactor, enabling the reaction solution to perform flow reaction in the transparent tube under the irradiation of visible light by the transparent tube at a flow rate of 5-20mL/min, and monitoring the reaction (2, 4-dinitrophenylhydrazine and potassium permanganate solution for color development) through a TLC plate until the reaction is complete.
9. A process of one-step preparation of nitrile compounds from different substituted cycloalkanones according to claim 8, wherein the flow rate of the continuous flow chemical reactor is 5-20 mL/min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647686A (en) * | 1981-08-31 | 1987-03-03 | Allied Corporation | Catalytic method of preparing keto-cyano alkane compounds |
| KR20180067888A (en) * | 2016-12-13 | 2018-06-21 | 인천대학교 산학협력단 | Heterogeneous copper-catalyzed aerobic oxidative conversion of aromatic aldehydes to corresponding nitriles |
| CN113801036A (en) * | 2021-10-23 | 2021-12-17 | 江西农业大学 | Method for preparing citranitrile by using litsea cubeba essential oil |
| CN113996322A (en) * | 2021-11-12 | 2022-02-01 | 鞍山七彩化学股份有限公司 | Catalyst for preparing dinitrile compound from alicyclic hydrocarbon and synthesis method of dinitrile |
| WO2022029583A1 (en) * | 2020-08-07 | 2022-02-10 | Inv Nylon Chemicals Americas, Llc | Production of dinitriles |
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- 2022-07-15 CN CN202210856278.3A patent/CN115093346B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4647686A (en) * | 1981-08-31 | 1987-03-03 | Allied Corporation | Catalytic method of preparing keto-cyano alkane compounds |
| KR20180067888A (en) * | 2016-12-13 | 2018-06-21 | 인천대학교 산학협력단 | Heterogeneous copper-catalyzed aerobic oxidative conversion of aromatic aldehydes to corresponding nitriles |
| WO2022029583A1 (en) * | 2020-08-07 | 2022-02-10 | Inv Nylon Chemicals Americas, Llc | Production of dinitriles |
| CN113801036A (en) * | 2021-10-23 | 2021-12-17 | 江西农业大学 | Method for preparing citranitrile by using litsea cubeba essential oil |
| CN113996322A (en) * | 2021-11-12 | 2022-02-01 | 鞍山七彩化学股份有限公司 | Catalyst for preparing dinitrile compound from alicyclic hydrocarbon and synthesis method of dinitrile |
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