CN106986754B - Method for preparing methyl ketone by cobalt catalysis - Google Patents
Method for preparing methyl ketone by cobalt catalysis Download PDFInfo
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- CN106986754B CN106986754B CN201710210300.6A CN201710210300A CN106986754B CN 106986754 B CN106986754 B CN 106986754B CN 201710210300 A CN201710210300 A CN 201710210300A CN 106986754 B CN106986754 B CN 106986754B
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- methyl ketone
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- alkyne
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- 238000000034 method Methods 0.000 title claims abstract description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 10
- 239000010941 cobalt Substances 0.000 title claims abstract description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 238000010898 silica gel chromatography Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims 1
- 150000001345 alkine derivatives Chemical class 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 230000002378 acidificating effect Effects 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 230000036632 reaction speed Effects 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 150000002923 oximes Chemical class 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 description 10
- 238000006460 hydrolysis reaction Methods 0.000 description 10
- 239000002253 acid Substances 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- -1 gold cations Chemical class 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 150000004032 porphyrins Chemical class 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002730 mercury Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- KBIAVTUACPKPFJ-UHFFFAOYSA-N 1-ethynyl-4-methoxybenzene Chemical group COC1=CC=C(C#C)C=C1 KBIAVTUACPKPFJ-UHFFFAOYSA-N 0.000 description 1
- ADLVDYMTBOSDFE-UHFFFAOYSA-N 5-chloro-6-nitroisoindole-1,3-dione Chemical compound C1=C(Cl)C([N+](=O)[O-])=CC2=C1C(=O)NC2=O ADLVDYMTBOSDFE-UHFFFAOYSA-N 0.000 description 1
- ZUKOCGMVJUXIJA-UHFFFAOYSA-N 6-chlorohex-1-yne Chemical compound ClCCCCC#C ZUKOCGMVJUXIJA-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
- C07C45/26—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydration of carbon-to-carbon triple bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/29—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of oxygen-containing functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/36—Oxygen or sulfur atoms
- C07D207/40—2,5-Pyrrolidine-diones
- C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
- C07D207/408—Radicals containing only hydrogen and carbon atoms attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
- C07D209/48—Iso-indoles; Hydrogenated iso-indoles with oxygen atoms in positions 1 and 3, e.g. phthalimide
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
Abstract
Aiming at the defects of high cost, harsh reaction conditions, environmental pollution and incapability of large-scale production in the prior art for preparing the methyl ketone catalyst. The invention particularly discloses a method for preparing methyl ketone by cobalt catalysis, which activates triple bonds in alkyne through Lewis acidity of metal cobalt coordinated with oxime, so that alkyne can be efficiently hydrolyzed into methyl ketone. Methanol is used as a solvent, the concentration of reaction substances is 0.25mol/L, a catalyst is added into a reaction system according to 5 percent of the molar weight of the raw materials, the reaction temperature is 65 ℃, and then the alkyne can be efficiently hydrolyzed into the methyl ketone. And the catalytic performance can be compared with other catalysts. The reaction temperature is mild, the reaction speed is high, and no acidic substance is required to be added in the reaction process. The environmental pollution is reduced to the minimum, the operation process of the reaction is simplified to the minimum, and the safety of operators and the feasibility of the reaction are guaranteed to the maximum. Therefore, the industrialization trend of the reaction is more obvious.
Description
Technical Field
The invention belongs to the field of chemistry, and particularly relates to a method for preparing methyl ketone by cobalt catalysis.
Background
Catalytic hydrolysis of alkynes is very important for functional group conversion. The key to this reaction is: the alkynyl atoms are economically and environmentally friendly converted to carbonyl compounds by suitable catalysts.
The reaction is usually carried out in an acidic medium as HgO-H2SO4(Kucherov catalyst) and HgO-BF3(Hennion-Nieuwland catalyst) as catalyst. However, environmental problems due to the toxicity of mercury salts have prevented their adequate use. Therefore, during the last decades researchers have made extensive studies on alkyne hydrolysis, including Rh catalysts, Ru catalysts, Pt catalysts, Ir catalysts, Pd catalysts, cu (ii) catalysts, fe (iii) catalysts, ag (i) catalysts, Au catalysts, on the catalytic performance of such reactions. And the conditions required for the hydrolysis of alkynes in the absence of metal were found to be very severe.
In recent years, since Au (I) [ Au (L)]+The very good reactivity and selectivity of (L ═ phosphine or L ═ N-heterocyclic carbene) catalysts has been one of the most promising catalysts for the hydrolysis of alkynes. However, this approach has some disadvantages, such as the metal and the ligand being expensive. Recently, Naka and Lin have made some breakthrough in the field, and they use co (iii) porphyrins and MOF complexes and cross-linked supported catalysts as catalysts for terminal alkyne hydrolysis, all of which react efficiently in the presence of acids, bases and even redox sensitive functional groups. However, porphyrin-based ligands (ca. nah)2TPPS) is too costly to be industrialized. There is therefore still a need for more economical and environmentally friendly catalytic systems with functional group compatibility.
The first prior art is as follows: HgO-H2SO4(Kucherov catalyst) catalyzes the process of hydrolysis. Not only does the need to add large amounts of sulfuric acid during the reaction, but also the environmental problems caused by the toxicity of mercury salts have hindered the application of this technology. The second prior art is: ferric and cupric iron catalyse the hydration process. Although some cheap metals can activate alkyne, the substrate application range is widerNarrower, some are only available under strongly acidic conditions, or are only available for alkynyl groups attached to aromatic systems. The scheme has the advantages of low reaction speed and poor functional group compatibility, thereby causing small application range. The prior art is three: catalytic hydrolysis without metal. The addition of large amounts of acid during the reaction leads to operational risks and to a smaller substrate application and to a substantial incompatibility of the acid-sensitive groups. The prior art is four: in the process of hydrolysis under the catalysis of gold cations, the reaction not only uses noble metals, but also has slightly high reaction temperature, poor cost performance and danger. The prior art is five: the process of hydrolysis is catalyzed using co (iii) porphyrins and MOF complexes thereof. This scheme is an improvement over the two previously mentioned, but the ligand is too expensive to industrialize. The prior art is six: some representative examples of other transition metals are Ru catalysts, Ir catalysts, and the like. As can be seen from the above examples, most metals as well as ligands are expensive and require the addition of acid, resulting in reduced functional group compatibility.
Disclosure of Invention
Aiming at the defects of high cost, harsh reaction conditions, environmental pollution and incapability of large-scale production of the catalyst in the prior art. The invention particularly discloses a method for preparing methyl ketone by cobalt catalysis, which activates triple bonds in alkyne through Lewis acidity of metal cobalt coordinated with oxime, so that alkyne can be efficiently hydrolyzed into methyl ketone. Methanol is used as a solvent, the concentration of reaction substances is 0.25mol/L, a catalyst is added into a reaction system according to 5 percent of the molar weight of the raw materials, the reaction temperature is 65 ℃, and then the alkyne can be efficiently hydrolyzed into the methyl ketone. And the catalytic performance can be compared with other catalysts. The reaction temperature is mild, the reaction speed is high, and no acidic substance is required to be added in the reaction process. The environmental pollution is reduced to the minimum, the operation process of the reaction is simplified to the minimum, and the safety of operators and the feasibility of the reaction are guaranteed to the maximum. Therefore, the industrialization trend of the reaction is more obvious.
The invention has the advantages that the cost of the used catalyst is very low, and the catalytic performance can be compared with other catalysts. The reaction temperature is mild, the reaction speed is high, and no acidic substance is required to be added in the reaction process. The environmental pollution is reduced to the minimum, the operation process of the reaction is simplified to the minimum, and the safety and the feasibility of operators are guaranteed to the maximum extent.
Detailed Description
Example 1
p-Chlorobenzeneacetylene (10g, 73.2mmol) was added to a 250mL round bottom flask containing a solution of methanol (117mL), magnetons were added, and after stirring well, catalyst (616mg, 1.46mmol) was added. The reaction was then heated to 65 ℃ and after 20h of reaction, quenched with water and the reaction flask cooled to room temperature. After the solvent was removed by evaporation, the mixture was separated by silica gel column chromatography to obtain a colorless oily liquid.
The reaction formula is as follows:
the following examples, which are examples of the hydrolysis of alkynes to methyl ketones, are useful in understanding the present invention. See example 1 for reaction conditions.
Example 2
0.25mmol of an aromatic system-linked alkynyl compound (e.g., phenylacetylene, p-methoxyphenylacetylene, etc.) was added to a 5mL round-bottom flask containing 1mL of a methanol solution, followed by addition of magnetons and, after stirring well, addition of 5 mol% of a catalyst thereto. The reaction was then heated to 65 ℃ and after 4.5h of reaction, quenched with water and the reaction flask cooled to room temperature. After the solvent was removed by evaporation, the mixture was separated by silica gel column chromatography to obtain a colorless oily liquid.
Example 3
0.25mmol of the acid-sensitive terminal alkyne compound (e.g., a compound containing Boc-, MOMO-, etc.) was placed in a 10mL sealed tube containing 1mL of methanol solution, magnetons were added, and after stirring well, 5 mol% of the catalyst was added thereto. Then heating the reaction system to 60 ℃, after reacting for 10-20h, quenching with water, and cooling the reaction bottle to room temperature. After the solvent was removed by evaporation, the mixture was separated by silica gel column chromatography to obtain a colorless oily liquid.
Example 4
0.25mmol of chain terminal alkyne compound (such as 6-chlorohexyne) is added into a 10mL sealed tube filled with 1mL of methanol solution, magnetons are added, and after uniform stirring, 2mol percent of catalyst is added. Then the reaction system was heated to 70 ℃ and after 10h of reaction, quenched with water and the reaction flask was cooled to room temperature. After the solvent was removed by evaporation, the mixture was separated by silica gel column chromatography to obtain a colorless oily liquid.
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (3)
1. A method for preparing methyl ketone by cobalt catalysis is characterized by comprising the following steps:
firstly, adding phenylacetylene into a round-bottom flask filled with a methanol solution;
secondly, adding magnetons, and stirring uniformly;
thirdly, adding a catalyst, and then heating the reaction system to 60-70 ℃;
fourthly, after 20 hours of reaction, quenching the mixture by water, and cooling the reaction bottle to room temperature;
fifthly, removing the solvent by spinning, separating by silica gel column chromatography to obtain colorless oily liquid,
the catalyst is selected from:
。
2. the method for preparing methyl ketone by catalysis of cobalt as claimed in claim 1, wherein the concentration of the reaction substance is 0.25mol/L, and the catalyst is added into the reaction system according to 5% of the molar weight of the raw materials.
3. The method for preparing methyl ketone by catalyzing cobalt as claimed in claim 1, wherein the reaction temperature is 65 ℃ after the catalyst is added.
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| CN201710210300.6A CN106986754B (en) | 2017-03-31 | 2017-03-31 | Method for preparing methyl ketone by cobalt catalysis |
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| CN201710210300.6A CN106986754B (en) | 2017-03-31 | 2017-03-31 | Method for preparing methyl ketone by cobalt catalysis |
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| CN106986754B true CN106986754B (en) | 2021-04-23 |
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| CN111170837B (en) * | 2020-01-02 | 2023-09-26 | 大连凯飞化学股份有限公司 | Synthesis method of methyl ketone compound |
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| US3860612A (en) * | 1968-03-20 | 1975-01-14 | Mobil Oil Corp | Preparation of polycyclic ketones |
| CN101624322B (en) * | 2009-08-05 | 2012-07-18 | 苏州大学 | Method for preparing 1, 2-diketone by catalyzing and oxidizing alkynes |
| CN104557499A (en) * | 2013-10-15 | 2015-04-29 | 南京理工大学 | Method for synthesizing methyl ketone |
| CN103524547B (en) * | 2013-11-02 | 2016-01-20 | 中国烟草总公司郑州烟草研究院 | A kind of sila medicinal herbs ketone and preparation method thereof |
| CN104529725B (en) * | 2014-12-11 | 2016-06-08 | 湖南大学 | The preparation method of perfluoro octyl sulfonic acid silver catalysis alkynes hydrolysis ketone |
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Non-Patent Citations (2)
| Title |
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| Compartmentalization of Incompatible Catalytic Transformations for Tandem Catalysis;J. Lu等;《J. Am. Chem. Soc.》;20151001(第137期);12984-12989 * |
| Evidence for Formation of a Co-H Bond from (H2O)2Co(dmgBF2)2 under H2: Application to Radical Cyclizations;Gang Li等;《J. Am. Chem. Soc.》;20120816(第134期);14662-14665 * |
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