CN107952459B - Method for synthesizing macrocyclic ketene, catalyst and application thereof - Google Patents
Method for synthesizing macrocyclic ketene, catalyst and application thereof Download PDFInfo
- Publication number
- CN107952459B CN107952459B CN201711288992.2A CN201711288992A CN107952459B CN 107952459 B CN107952459 B CN 107952459B CN 201711288992 A CN201711288992 A CN 201711288992A CN 107952459 B CN107952459 B CN 107952459B
- Authority
- CN
- China
- Prior art keywords
- benzene ring
- catalyst
- macrocyclic
- ketone
- hypochlorite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- 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
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
-
- 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
- C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a synthesis method of macrocyclic ketene, a catalyst and application thereof, and the catalyst for synthesizing macrocyclic ketene provided by the invention comprises a carrier, and transition metal and Bronsted acid loaded on the carrier; the carrier is a metal oxide; preferably, the loading of the bronsted acid on the support is from 1 to 10%, the loading of the transition metal is from 0.1 to 10%, and the loading of the transition metal is more preferably from 1 to 5%, based on the mass of the catalyst. The catalyst of the invention is used for catalyzing macrocyclic ketone to synthesize macrocyclic ketene, and has the advantages of simple preparation process, convenient operation, easy large-scale production and the like.
Description
Technical Field
The invention relates to the technical field of preparation of macrocyclic ketene, and particularly relates to a catalyst and a method for preparing macrocyclic ketene by catalyzing dehydrogenation of macrocyclic ketone by using the catalyst.
Background
Many macrocyclic ketenes have a very elegant musk aroma, such as natural civetone (9-cyclopentadecanone), and the artificially synthesized naturally occurring musks (3-methyl-5-cyclotetradecenone), musk ketenes (3-methyl-5-cyclopentadecanone), 5-cyclohexadecanone, 8-cyclohexadecanone, and the like. Compared with saturated macrocyclic ketones, these macrocyclic ketenes have a musk odour close to the threshold value, and due to the presence of double bonds, macrocyclic ketenes are more easily degraded and have better biocompatibility. In addition, some macrocyclic enones are important intermediates, such as 2-cyclopentadecanone, which can be reacted with methyl grignard reagents to conveniently synthesize natural muscone (3-methylcyclopentadecanone).
When the cyclic ketene is prepared, saturated cyclic ketone is used as an initial raw material, and the cyclic ketene can be synthesized very efficiently and quickly through oxidation or dehydrogenation reaction. At present, documents (Regio-and Enantio-selective Enolisates of cyclic Ketone Using Chiral Lithium Amide Bases, J.chem.Soc.Perkin Trans.1,1995,2535-2541) report that dehydrogenation of cyclohexanone derivatives to cyclohexenone products is achieved by two-step reactions of enol silicon etherification and palladium oxidation using equivalent amounts of aminolithium reagents. In another document (iodine (V) Reagents in organic Synthesis, part 4.o-Iodoxybenzoic Acid as a Chemospecific Tool for Single Electron Transfer-Based Oxidation process, J.Am.chem.Soc.,2002,124, 2245-Acid 2258) it is reported that the Oxidation of cyclodecanone, cycloundecanone, cyclopentadecanone is achieved using an equivalent amount of 2-Iodoxybenzoic Acid as the oxidizing agent, and the corresponding cyclic enone product is obtained in moderate to good yields. All the reports adopt equivalent organic reagents to realize dehydrogenation, and the used organic reagents are expensive, cannot be recycled and have high economic cost.
There are some documents reporting that Dehydrogenation of Cyclic Ketones is achieved by catalytic oxidation, for example, there are documents (Aerobic Dehydrogenation of Cyclic Ketones in coresponding phenols catalyzed by heterocyclic Pd Nanocatalysts, catalysis, communications,2017,89,60-63) reporting that Dehydrogenation of cyclohexanone is achieved by using nano-palladium as a catalyst, and a mixture of cyclohexenone and phenol is obtained in a moderate yield. There is also literature (aerobiotic dehydration of cyclic quinone to phenolic catalysis)by Pd(TFA)2An evaluation for the Role of PdNanoparticles, J.Am.chem.Soc.,2013,135,8213-8221) reports that the selective dehydrogenation of cyclohexanone can be realized by using homogeneous palladium as a catalyst and regulating and controlling a ligand and a reaction solvent to respectively obtain cyclohexenone and phenol products, but substrates are limited to cyclohexanone, and the dosage of the catalyst is larger (3-5 mol%).
In general, there are very few reports on the dehydrogenation synthesis of cyclic ketones to prepare cyclic ketenes in the field, and these reports either use expensive high-valent iodine oxidants or require high catalytic amounts of noble metals, and the substrate range is mostly limited to cyclohexanone and its derivatives.
As the macrocyclic ketene is widely applied in the field of flavors and fragrances and is an important synthetic intermediate, the development of the process for synthesizing the macrocyclic ketene by dehydrogenating the macrocyclic ketone, which is simple in operation, economic and environment-friendly, has important significance.
Disclosure of Invention
The invention provides a catalyst for synthesizing macrocyclic ketene and a method for preparing macrocyclic ketene by using the catalyst to catalyze the dehydrogenation of macrocyclic ketone, so as to make up the defects of the prior art. The catalyst of the invention is used for catalyzing macrocyclic ketone to synthesize macrocyclic ketene, and has the advantages of simple preparation process, convenient operation, easy large-scale production and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a catalyst for synthesizing macrocyclic ketene, which comprises a carrier, a transition metal and a Bronsted acid, wherein the transition metal and the Bronsted acid are loaded on the carrier; the carrier is a metal oxide.
The catalyst of the invention is used for catalyzing the dehydrogenation of the macrocyclic ketone to synthesize the macrocyclic ketene, and has the characteristics of simple reaction process, less by-products, easy large-scale production and the like.
In the catalyst of the present invention, it is preferable that the loading amount of the bronsted acid on the carrier is 1 to 10% and the loading amount of the transition metal is 0.1 to 10% based on the mass of the catalyst. In a further preferred embodiment, the transition metal is more preferably supported in an amount of 1 to 5%.
In the catalyst of the invention, the carrier is preferably one or at least two of magnesium oxide, calcium oxide, silicon oxide, titanium oxide and aluminum oxide, more preferably aluminum oxide, and preferably aluminum oxide, has strong acidity, can promote the isomerization of substrate enol, and is beneficial to the dehydrogenation reaction.
In the catalyst of the present invention, the transition metal is preferably one or at least two of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and copper, and more preferably nickel, so as to achieve better dehydrogenation activity and stability and promote the rapid completion of dehydrogenation reaction.
In the catalyst, the Bronsted acid is preferably one or at least two of phosphoric acid, sulfuric acid, perchloric acid and nitric acid, and is further preferably phosphoric acid, so that the isomerization of a substrate is accelerated, the coordination of the substrate and metal is promoted, and the conversion rate and the selectivity are improved; in a more preferable scheme, the bronsted acid in the catalyst is phosphoric acid, and the transition metal is nickel, so that the combination of the bronsted acid and the nickel can obtain better catalytic activity, and the conversion rate, the selectivity and the dehydrogenation reaction rate are higher.
The catalyst of the invention can be prepared by a coprecipitation method, an impregnation method, an ion exchange method and other process methods known in the art, more preferably by the impregnation method, and the preparation is simple and easy to obtain.
In a second aspect, the present invention provides a process for the synthesis of a macrocyclic enone, comprising the steps of catalyzing the dehydrogenation of a macrocyclic ketone of the formula (I) as described hereinbefore in the presence of a catalyst as described herein to form the corresponding macrocyclic enone:
wherein R in the formula (I) is hydrogen, alkyl of C1-C20, naphthyl, phenyl or benzene ring containing substituent groups. Preferably, R may be located at positions α, β, γ, ω, etc. of the carbonyl group. The formula (I) is in particular a macrocyclic ketone with an R substituent in the ring, which contains 10 to 18 carbon atoms in the ring.
In the synthesis method of the present invention, preferably, when R in formula (I) is a substituted benzene ring, the benzene ring may be a mono-substituted or poly-substituted benzene ring, where the meaning of "poly" in "poly" refers to two or more (including the present number of two), and the poly-substituted benzene ring is, for example, a di-substituted, tri-substituted or tetra-substituted benzene ring, etc. When the benzene ring is mono-substituted, the substituent on the benzene ring is methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl; when the phenyl ring is a polysubstituted phenyl ring, a plurality of substituents on the phenyl ring are the same or different from each other, and each substituent is independently selected from methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl.
In the synthesis method, hypochlorite is preferably used as an oxidant in the reaction system, the hypochlorite is preferably selected from one or more of lithium hypochlorite, sodium hypochlorite, potassium hypochlorite and calcium hypochlorite, and more preferably the calcium hypochlorite, so that the cost is low, and the reaction speed is high; preferably, the amount of hypochlorite used is from 40 to 150%, more preferably from 50 to 110% of the amount of macrocyclic ketone material.
In a preferred embodiment of the synthesis method of the present invention, the macrocyclic ketene prepared comprises one or more of an α, β -unsaturated ketone or an α, β -diunsaturated ketone. The type of product can be controlled by the amount of the oxidizing agent (e.g., calcium hypochlorite), for example, alpha, beta-unsaturated ketones can be obtained when 0.5 equivalent of calcium hypochlorite is added relative to the macrocyclic ketone substrate, and alpha, beta-diunsaturated ketones can be obtained when 1 equivalent or more of calcium hypochlorite is added.
Further, in a preferred embodiment, the α, β -unsaturated ketone has the following structural formula (II) and the α, β -diunsaturated ketone has the following structural formula (III):
r in the formula (II) or the formula (III) is hydrogen, C1-C20 alkyl, naphthyl, phenyl or a benzene ring containing a substituent; preferably, the benzene ring containing the substituent is a mono-substituted or poly-substituted benzene ring, and when the benzene ring is a mono-substituted benzene ring, the substituent on the benzene ring is methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl; when the benzene ring is polysubstituted, a plurality of substituents on the benzene ring are respectively and independently selected from methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl.
According to the synthesis method, the dehydrogenation reaction is preferably carried out in the presence of a solvent, the solvent is further preferably one or more selected from toluene, xylene, N-dimethylformamide, acetic acid and dimethyl sulfoxide, more preferably acetic acid, and the yield of the prepared target product is high.
In the synthesis method of the present invention, the amount of the catalyst used is preferably 0.1 to 10%, more preferably 1 to 5%, of the amount of the macrocyclic ketone substance, based on the transition metal contained in the catalyst.
In the synthesis method of the invention, the temperature of the dehydrogenation reaction of the macrocyclic ketone is preferably 80-160 ℃, more preferably 90-110 ℃ so as to achieve higher reaction yield.
In the synthesis method of the present invention, the dehydrogenation reaction of the macrocyclic ketone is preferably carried out in an oxygen-containing gas atmosphere, for example, in air, oxygen or another mixed gas containing oxygen, and more preferably in an oxygen atmosphere.
The technical scheme provided by the invention has the following beneficial effects:
1. the catalyst for synthesizing the macrocyclic ketene has the characteristics of small catalyst dosage, high selectivity, few byproducts and the like, is economical, environment-friendly and easy to operate, and is suitable for the large-scale synthesis of the macrocyclic ketene.
2. The catalyst of the invention has simple preparation process and easy amplification synthesis, and the separation of the catalyst and the product can be realized by simple filtration after the reaction is finished. In addition, by adjusting the addition of the oxidant hypochlorite, the invention can also realize the regulation and control of oxidation products and selectively obtain the alpha, beta-unsaturated ketone or the alpha, beta-double unsaturated ketone. .
3. The ketene product obtained by the synthesis method has high purity and good fragrance, can be used as a synthesis intermediate, and can also be directly used in the fields of essence, spice, cosmetics and the like.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The reagents used in the examples are described below:
Ni(acac)2(98wt％)，RuCl3(98wt％)，CoCl2(98 wt%), Aldrich; phosphoric acid (85 wt%), sulfuric acid (98 wt%), perchloric acid (70%), ethanol (AR), chinese medicine reagents; calcium hypochlorite (98 wt%), sodium hypochlorite (98 wt%); alumina (300-400 meshes, 99 wt%), silica (300-400 meshes, 98 wt%), titanium oxide (300-400 meshes, 97 wt%), acetic Acid (AR), decalin (99 wt%), and an avadin reagent; cyclodecanone (97 wt%), cyclododecanone (99 wt%), cyclotridecanone (98 wt%), cyclopentadecanone (98 wt%), cyclohexadecanone (98 wt%), Annagel chemistry; 3-methylcyclopentadecanone (96 wt%), prepared in the laboratory.
The gas chromatography test conditions used in the examples were as follows:
the instrument model is as follows: SHIMADZU GC-2010-plus;
a chromatographic column: DB-5(30m 0.25mm 0.25 μm);
column temperature: the initial temperature is 50 ℃, the temperature is raised to 150 ℃ at the speed of 15 ℃/min, the temperature is maintained for 5min, then the temperature is raised to 280 ℃ at the speed of 20 ℃/min, and the temperature is maintained for 10 min;
sample inlet temperature: 220 ℃;
FID detector temperature: 300 ℃;
split-flow sample injection with a split-flow ratio of 50: 1;
sample introduction amount: 2.0 mu L;
N2flow rate: 40 mL/min;
H2flow rate: 400 mL/min.
The nuclear magnetic instruments used in the examples were: bruker Avance Neo,400 MHz.
Example 1: catalyst preparation
Preparing an alumina-supported nickel-phosphoric acid catalyst by adopting an impregnation method: weighing Ni (acac)2(17.52g) phosphoric acid (85 wt%) (11.76g), rapid (600-800 rpm)) Dissolving in ethanol (400mL) under stirring to obtain a uniform solution; then (186.00g) alumina powder (300-400 meshes) is added, the mixture is soaked for 6 hours, the water bath is slowly stirred (200 r/min) to evaporate the ethanol, the obtained solid powder is dried at 80 ℃, the solid powder is decomposed in vacuum at 300 ℃ for 2 hours, then hydrogen is introduced to reduce the solid powder for 2 hours, and the nickel-phosphoric acid catalyst loaded on the alumina is obtained through tabletting, crushing and screening. The mass fraction of nickel supported in the catalyst was 2% and the mass fraction of phosphoric acid was 5%, based on the mass of the catalyst, and the catalyst was named 2% Ni-5% H3PO4/Al2O3。
Examples 2 to 11: catalyst preparation
Different catalysts can be prepared by changing the transition metal, the Bronsted acid, the carrier and the like by the same catalyst preparation method as in example 1, and the specific application is shown in the following table. Catalyst designation 1% Ni-5% H3PO4/Al2O3For example, 1% represents the mass fraction of nickel in the catalyst, 5% represents the mass fraction of phosphoric acid, Al2O3The catalyst support is shown.
TABLE 1 dehydrogenation catalyst
Example 12
In the air, the alumina-supported nickel-phosphoric acid catalyst obtained in example 1 (used in an amount to give a Ni content of 0.01mol), cyclododecanone (1.0mmol), acetic acid (3.0mL) and calcium hypochlorite (0.55mol) were sequentially added to a 50mL reaction flask, and the reaction flask was put in an oil bath at 100 ℃ and reacted with rapid (800 rpm) stirring for 12 hours. After the reaction, the reaction solution was cooled to room temperature, filtered, and an internal standard substance (decahydronaphthalene) was added, followed by gas chromatography analysis of the reaction solution to determine that the yield of cyclododecadienone was 91%, and the product was a cis-trans mixture of cyclododecadienone. The nuclear magnetic information of the product is as follows:1H-NMR(400MHz,CDCl3):6.78(dt,J＝15.8,7.6Hz,1H),6.30(dt,J＝15.8Hz,1H),2.48(t,J＝6.6Hz,2H),2.25(qd,J＝4.8Hz,2H),1.73(q,J＝6.6Hz,2H)；1.69-1.54(m,2H),1.46-1.22(m,10H)。
the basic reaction equation of this example is as follows:
examples 13 to 23
Examples 13-23 were prepared essentially identically to example 12, except that the catalyst used was different, as specified in Table 2. Each catalyst was derived from the corresponding catalyst prepared in examples 1-11.
The cyclododecenone yields of examples 13 to 23 are shown in Table 2.
TABLE 2 optimization of cyclododecanone dehydrogenation reaction conditions
aCyclododecanone (1.0mmol), 2% Ni-5% H3PO4/Al2O3(0.01mmol Ni), calcium hypochlorite (0.55mol), acetic acid (3.0 mL).bYield of internal standard, decahydronaphthalene is internal standard substance.cSodium hypochlorite (1.1 mol).
Examples 24-30 substrate extension
2% Ni-5% H in air3PO4/Al2O3(the amount was such that the Ni content was 0.01mmol), macrocyclic ketone (1.0mmol), calcium hypochlorite (0.55mmol), and acetic acid (3.0mL) were sequentially added to a 50mL reaction flask, and the reaction flask was put in a 100 ℃ oil bath and reacted for 12 hours with rapid (800 rpm) stirring. After the reaction is finished, cooling the reaction liquid to room temperature, filtering, and directly separating the product by column chromatography.
The yields of the macrocyclic ketones used in examples 24-30 and the desired products of the respective examples are shown in Table 3; the products of the examples are confirmed to obtain target products through nuclear magnetic analysis, and details are not repeated.
The basic reaction equation for examples 24-30 is shown below:
TABLE 3 substrate expansion for the dehydrosynthesis of macrocyclic ketenes from macrocyclic ketones
Examples 31-36 substrate expansion
2% Ni-5% H in air3PO4/Al2O3(the amount was such that the Ni content was 0.01mmol), macrocyclic ketone (1.0mmol), calcium hypochlorite (1.1mmol) and acetic acid (3.0mL) were sequentially added to a 50mL reaction flask, and the reaction flask was put in an oil bath at 100 ℃ and reacted for 24 hours with rapid (800 rpm) stirring. After the reaction is finished, cooling the reaction liquid to room temperature, filtering, and directly separating the product by column chromatography.
The yields of macrocyclic ketones used in examples 31 to 36 and the target products of the examples are specifically shown in table 4, and the target products are confirmed to be obtained by nuclear magnetic analysis of the products of the examples, which is not described in detail.
The basic reaction equation for examples 31-36 is shown below:
TABLE 4 substrate expansion for the dehydrosynthesis of macrocyclic ketenes from macrocyclic ketones
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (17)
1. A catalyst for synthesizing macrocyclic ketene, which is characterized in that the catalyst comprises a carrier, and a transition metal and a bronsted acid which are loaded on the carrier; the carrier is a metal oxide; the transition metal is one or at least two of iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum and copper; the loading of the bronsted acid on the carrier is 1-10% and the loading of the transition metal is 0.1-10% based on the mass of the catalyst.
2. The catalyst of claim 1, wherein the transition metal loading is 1-5%.
3. The catalyst according to claim 1, wherein the carrier is one or at least two of magnesium oxide, calcium oxide, silicon oxide, titanium oxide and aluminum oxide.
4. A catalyst according to any one of claims 1 to 3, characterised in that the transition metal is nickel.
5. The catalyst according to any one of claims 1 to 3, wherein the Bronsted acid is one or at least two of phosphoric acid, sulfuric acid, perchloric acid, nitric acid.
6. The catalyst according to claim 5, characterized in that the Bronsted acid is phosphoric acid.
7. A process for the synthesis of a macrocyclic enone, comprising the step of catalysing the dehydrogenation of a macrocyclic ketone of the formula (I) as defined in any one of claims 1 to 6 to give the corresponding macrocyclic enone:
wherein R in the formula (I) is hydrogen, alkyl of C1-C20, naphthyl, phenyl or benzene ring containing substituent groups.
8. The synthesis method of claim 7, wherein the benzene ring containing the substituent is a mono-substituted or poly-substituted benzene ring, and when the benzene ring is a mono-substituted benzene ring, the substituent on the benzene ring is methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl; when the benzene ring is polysubstituted, a plurality of substituents on the benzene ring are respectively and independently selected from methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl.
9. The synthesis method according to claim 7, wherein hypochlorite is used as an oxidizing agent in the reaction system, and the hypochlorite is selected from one or more of lithium hypochlorite, sodium hypochlorite, potassium hypochlorite and calcium hypochlorite.
10. A process according to claim 9, wherein the amount of hypochlorite used is 40-150% of the amount of macrocyclic ketone substance.
11. The synthetic method of claim 7, wherein the macrocyclic enone comprises one or more of an α, β -unsaturated ketone or an α, β -diunsaturated ketone.
12. The method of synthesis of claim 11, wherein the α, β -unsaturated ketone has the following structural formula (II) and the α, β -diunsaturated ketone has the following structural formula (III):
r in the formula (II) or the formula (III) is hydrogen, C1-C20 alkyl, naphthyl, phenyl or a benzene ring containing a substituent.
13. The synthesis method of claim 12, wherein the benzene ring containing the substituent is a mono-substituted or poly-substituted benzene ring, and when the benzene ring is a mono-substituted benzene ring, the substituent on the benzene ring is methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl; when the benzene ring is polysubstituted, a plurality of substituents on the benzene ring are respectively and independently selected from methyl, methoxy, benzyloxy, fluorine, chlorine, trifluoromethyl or methoxycarbonyl.
14. The synthesis method according to claim 7, wherein the dehydrogenation reaction is carried out in the presence of a solvent selected from one or more of toluene, xylene, N-dimethylformamide, acetic acid, and dimethylsulfoxide.
15. The process of claim 7, wherein the catalyst is present in an amount of 0.1 to 10% based on the amount of macrocyclic ketone material present in the catalyst.
16. The synthesis process according to claim 7, characterized in that the temperature of the dehydrogenation reaction of the macrocyclic ketone is between 80 and 160 ℃.
17. The synthesis process according to claim 7, wherein the dehydrogenation reaction of the macrocyclic ketone is carried out in an atmosphere containing oxygen.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711288992.2A CN107952459B (en) | 2017-12-07 | 2017-12-07 | Method for synthesizing macrocyclic ketene, catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711288992.2A CN107952459B (en) | 2017-12-07 | 2017-12-07 | Method for synthesizing macrocyclic ketene, catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107952459A CN107952459A (en) | 2018-04-24 |
| CN107952459B true CN107952459B (en) | 2020-08-28 |
Family
ID=61958307
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711288992.2A Active CN107952459B (en) | 2017-12-07 | 2017-12-07 | Method for synthesizing macrocyclic ketene, catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107952459B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110227512B (en) * | 2019-06-17 | 2022-01-07 | 万华化学集团股份有限公司 | Preparation method and application of catalyst for preparing unsaturated ketone by Saucy-Marbet reaction |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3476808A (en) * | 1967-05-17 | 1969-11-04 | Mobil Oil Corp | Catalytic oxidative dehydrogenation of ketones |
| GB1340611A (en) * | 1969-10-16 | 1973-12-12 | Leuna Werke Veb | Process for the production of alpha, beta und alpha, beta, alpha,beta,-unsaturated ketones |
| US4933507A (en) * | 1987-12-03 | 1990-06-12 | Mitsui Petrochemical Industries, Inc. | Method of dehydrogenating cyclohexenone |
| CN1343191A (en) * | 1999-03-12 | 2002-04-03 | 巴斯福股份公司 | Method of producing cyclic, bata-unsaturated ketones |
| CN1425499A (en) * | 2001-12-11 | 2003-06-25 | 中国科学院大连化学物理研究所 | Solid supported noble metal catalyst and its preparing method |
| CN102553592A (en) * | 2012-03-18 | 2012-07-11 | 吉林大学 | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof |
| CN103058841A (en) * | 2013-01-08 | 2013-04-24 | 河南师范大学 | Preparation method of alpha-damascenone perfume |
| CN101959837B (en) * | 2008-02-28 | 2014-05-21 | 巴斯夫欧洲公司 | Method for producing olefinically saturated carbonyl compounds by oxidative dehydrogenation of alcohols |
-
2017
- 2017-12-07 CN CN201711288992.2A patent/CN107952459B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3476808A (en) * | 1967-05-17 | 1969-11-04 | Mobil Oil Corp | Catalytic oxidative dehydrogenation of ketones |
| GB1340611A (en) * | 1969-10-16 | 1973-12-12 | Leuna Werke Veb | Process for the production of alpha, beta und alpha, beta, alpha,beta,-unsaturated ketones |
| US4933507A (en) * | 1987-12-03 | 1990-06-12 | Mitsui Petrochemical Industries, Inc. | Method of dehydrogenating cyclohexenone |
| CN1343191A (en) * | 1999-03-12 | 2002-04-03 | 巴斯福股份公司 | Method of producing cyclic, bata-unsaturated ketones |
| CN1425499A (en) * | 2001-12-11 | 2003-06-25 | 中国科学院大连化学物理研究所 | Solid supported noble metal catalyst and its preparing method |
| CN101959837B (en) * | 2008-02-28 | 2014-05-21 | 巴斯夫欧洲公司 | Method for producing olefinically saturated carbonyl compounds by oxidative dehydrogenation of alcohols |
| CN102553592A (en) * | 2012-03-18 | 2012-07-11 | 吉林大学 | High-dispersion silicon-loaded Cu-based catalyst and preparation method thereof |
| CN103058841A (en) * | 2013-01-08 | 2013-04-24 | 河南师范大学 | Preparation method of alpha-damascenone perfume |
Non-Patent Citations (2)
| Title |
|---|
| Catalytic conversion of substituted and un-substituted cyclohexanone into corresponding enones and phenols by nanocatalysts under acid or base-free reaction conditions;Mazloom Shah等;《Applied Catalysis A: General》;20161101;第531卷;全文 * |
| 磷改性对氯化Ni-W/SiO2/γ-Al2O3降烯烃催化剂性能的影响;王吉林等;《工业催化》;20070228;第15卷(第2期);摘要，1.2节，2.2节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107952459A (en) | 2018-04-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cadierno et al. | Metal-catalyzed transformations of propargylic alcohols into α, β-unsaturated carbonyl compounds: from the Meyer–Schuster and Rupe rearrangements to redox isomerizations | |
| Levine et al. | Catalytic enantioselective approach to the eudesmane sesquiterpenoids: total synthesis of (+)-carissone | |
| CN107253937B (en) | A kind of synthetic method of gamma-valerolactone | |
| CN107522583B (en) | Cyclic economic process for the preparation of unsaturated compounds | |
| JP6074858B2 (en) | Process for producing unsaturated alcohol | |
| Kaizuka et al. | Multiphase flow systems for selective aerobic oxidation of alcohols catalyzed by bimetallic nanoclusters | |
| Takei et al. | CeO2-supported Pd (II)-on-Au nanoparticle catalyst for aerobic selective α, β-desaturation of carbonyl compounds applicable to cyclohexanones | |
| WO2016199174A1 (en) | Oxidative dehydrogenation of lactate esters to pyruvate esters | |
| Ren et al. | Ruthenium-Catalyzed Oxidation of Allyl Alcohols with Intermolecular Hydrogen Transfer: Synthesis of α, β-Unsaturated Carbonyl Compounds | |
| Shah et al. | One pot menthol synthesis via hydrogenations of citral and citronellal over montmorillonite-supported Pd/Ni-heteropoly acid bifunctional catalysts | |
| CN106866360A (en) | A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD | |
| CN105837416A (en) | Method for preparing aldehyde or ketone by alcohol selective oxidation under catalysis of copper complex | |
| CN107952459B (en) | Method for synthesizing macrocyclic ketene, catalyst and application thereof | |
| CN100522911C (en) | Preparation method for acetophenone | |
| EP2953920B1 (en) | Process for the isomerisation of an exo double bond | |
| CN108191635B (en) | Method for preparing gluconic acid by catalytic oxidation | |
| CN116943710B (en) | Metal supported catalyst, preparation method and application thereof in Diels-Alder reaction | |
| Suzuki et al. | Catalytic asymmetric Michael reactions using a chiral rhodium complex | |
| JP4862162B2 (en) | Catalyst for hydrogenation of carbonyl group, method for producing the same, and method for producing unsaturated alcohol using the catalyst | |
| JP4649743B2 (en) | Process for producing macrocyclic ketone compounds | |
| CN107827723B (en) | Long-chain diketone synthesis method | |
| Tsuji et al. | Synthesis of 2, 15-hexadecanedione, a precursor of muscone, from butadiene | |
| WO2006017970A1 (en) | Method for convertion of terminal alkenes to aldehydes using ruthenium(iv) porphrin catalysts | |
| CN110683930B (en) | Synthesis method of trans-stilbene | |
| US7034188B2 (en) | Production method of ketone compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |