GB2590589A - A synthetic method of a cycloketone compound - Google Patents

A synthetic method of a cycloketone compound Download PDF

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GB2590589A
GB2590589A GB2105879.7A GB202105879A GB2590589A GB 2590589 A GB2590589 A GB 2590589A GB 202105879 A GB202105879 A GB 202105879A GB 2590589 A GB2590589 A GB 2590589A
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compound
substituent groups
cycloketone
synthetic method
cycloalkane
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Chen Huarong
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Hangzhou Junling Pharmaceutical Tech Co Ltd
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Hangzhou Junling Pharmaceutical Tech Co Ltd
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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
    • 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
    • B01J27/24—Nitrogen compounds
    • B01J27/25—Nitrates
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/006—Catalysts comprising hydrides, coordination complexes or organic compounds comprising organic radicals, e.g. TEMPO
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235—Nitrogen containing compounds
    • B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B41/00—Formation or introduction of functional groups containing oxygen
    • C07B41/06—Formation or introduction of functional groups containing oxygen of carbonyl groups
    • 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
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/385—Saturated compounds containing a keto group being part of a ring
    • C07C49/403—Saturated compounds containing a keto group being part of a ring of a six-membered ring
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
    • B01J2531/37—Lanthanum
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/30—Non-coordinating groups comprising sulfur
    • 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
    • B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
    • B01J2540/40—Non-coordinating groups comprising nitrogen
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

A method for preparing cycloketones, wherein the method is listed as follows: under an oxygen-containing atmosphere, the corresponding cycloketone is synthesised from a cycloalkane by oxidation using a catalytic system, comprising dilute sulfuric acid, organic nitroxyl radical precursor and lanthanum metal; a composite catalyst system comprising the nitroxyl radical ligand and the lanthanum metal, and then aminoxyl radical is generated by a reaction of the nitroxyl radical ligand and the oxygen, thereby an intermediate is formed by combining with La3+, and then cooperated with the oxygen, the cycloalkane forms cycloalkyloxy lanthanum intermediate, thereby to react with the nitroxyl radical to form the cycloketone compound; thereby the conversion of the cycloalkane compound under moderate condition is improved, and then the selectivity of the ketone compound by ensuring a certain conversion of the cycloalkane compound. Preferably, the lanthanum compound is a salt, more preferably lanthanum (III) nitrate. Preferably, the organic nitroxyl radical precursor is a compound of formula (I), (II), (III) or (IV): wherein R in each formula is selected from hydrogen, alkyl, cycloalkyl, aryl, heterocycle, hydroxy, nitryl or halogen. Preferred cycloketones to be synthesised include cyclohexanone from cyclohexane and adamantanone from adamantane.

Description

A SYNTHETIC METHOD OF A CYCLOKETONE COMPOUND
TECHNICAL FIELD
[0001] The present invention relates to the technical field of organic synthesis in particular to a synthetic method of a cycloketone compound.
BACKGROUND OF THE INVENTION
[0002] Cycloketone compound is important chemical material which is widely used in some industries like synthetic rubber, industrial coating for fibre, pharmacy, pesticides and organic solvent; for example, cyclohexanone is used to prepare caprolactone, adipic acid and epsiloncaprolactam, or to be used as solvent and emulgator; recently, processing to product the cyclohexanone mainly has three kinds: liquid phase oxidation process of cyclohexane, the hydrogenation of phenol and partial hydrogenation of cyclohexane, wherein the liquid phase oxidation process of cyclohexane is the main process to product the cyclohexanone with over 90% proportions; however, the production process is regarded one of the chemical industrial process with the lowest efficiency.
[0003] On an industry, the liquid phase oxidation process of cyclohexane has three methods: (1) catalytic oxidation by taking cobalt salt as catalyst, the method is relative high in conversion rate, however, as adipic acid, cobalt salt produced is easily to cause reaction kettle fouling, thereby the method has been basically abandoned; (2) nitrose catalytic oxidization has a high investment of capital construction, high energy consuming, complex technique, difficult operation, which is easy causing reaction equipment and pipe heavily being blocked; (3) non-catalyst oxidization with air is effectively avoid fouling problems, however, the technique is complex in technique with much middle steps, conversion of the cyclohexane is low with high energy-consuming, furthermore, a large amount of spent lye produced in the process is difficult to be settled, which is still a hard issue for world environmental protection.
[0004] Patent CN109232209B discloses an oxidization method of alkane compound: under oxygen atmosphere, corresponding cycloketone compound and cyclitol compound are prepared by the cycloalkane compound through catalytic system, wherein the catalytic system comprises ring organic aminoxyl radical processor and cerate metal, wherein a conversion of the hexamethylene is 6.5-9.3% and a selectivity of the cyclohexanone is 80.5%.
BRIEF SUMMARY OF THE INVENTION
[0005] The present invention provide a synthetic method of a cycloketone compound so as to overcome the existing technical problems.
[0006] The following technical plan is adopted by the invention to solve the above-mentioned technical problems: [0007] A synthetic method of a cycloketone compound, wherein the synthetic method is listed as follows: under an oxygen-containing atmosphere, corresponding cycloketone compound is oxidized and synthesized from cycloalkane through a catalytic system, wherein the catalytic system comprises dilute sulfuric acid, organic nitroxyl radical precursor and lanthanum metal.
[0008] The synthetic method of a cycloketone compound defined in claim 1, wherein the organic nitroxyl radical precursor is selected from the following structures in formulaS (I),(H) ,(III) or (IV): (I) (I) (IV) 3 wherein R in formula is selected from hydrogen atom, alkyl, cycloalkyl, my], heterocycle, hydroxy, nitryl or halogens [0009] The synthetic method of a cycloketone compound defined in claim 1, wherein the lanthanum metal is one of lanthanum nitrate hydrate, lanthanum chloride and lanthanum acetate.
[0010] The synthetic method of a cycloketone compound defined in claim 1, wherein a concentration of the dilute sulfuric acid is 0.05mol/L-3mol/L.
[0011] The organic nitroxyl radical precursor in the present invention is able to catalyze cycloalkane compound oxidized under oxygen atmosphere by accompanying with the lanthanum metal, thereby corresponding of the cycloketone compound is generated with a high selectivity; for example, if substrate(material) is cyclopentane, thereby corresponding of the cycloketone compound is cyclopentanone; if the substrate is cyclohexane, thereby corresponding of the cycloketone compound is cyclohexanone.
[0012] After experiment, ring organic aminoxyl radical processor in formula structure is able to initiate the substrate to produce alkyl radical, and then to cooperate with the lanthanum metal to reacted with each other, which is benefit to improve a conversion of the substrate and total selectivity of the product.
[0013] Several kinds of the organic nitroxyl radical precursor mentioned before defined in the present invention are able to cooperate with the lanthanum metal to generate free radials by breaking C-H bonding of the cycloalkane; the free radials are able to generate ketone compounds after being oxidized by the lanthanum metal [0014] As an optimized technical proposal, nitroxyl radical ligand precursor is selected from at least one of the following formula (a)-(d): (a) (c) (d) [0015] The cycloalkane is taken as material, wherein the cycloalkane is a saturated hydrocarbons compound and derivatives thereof contains one or more rings with 3-18 carbon atoms in molecular structure.
[0016] Specifically, the cycloalkane is selected from at least one of cyclopentane compound, hexamethylene compound, cycloheptane compound, cyclooctane compound or adamantane, but not limited to the aforementioned ranges; [0017] The cyclopentane compound has 0-5 substituent groups, which can be either the cyclopentane or the cyclopentane containing 1-5 substituent groups, the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together; [0018] The hexamethylene compound has 0-6 substituent groups, which can be either the hexamethylene or the hexamethylene containing 1-6 substituent groups; the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together, [0019] The cycloheptane compound has 0-7 substituent groups, which can be either the cycloheptane or the cycloheptane containing 1-7 substituent groups; the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together; [0020] The cyclooctane compound has 0-8 substituent groups, which can be either the cyclooctane or the cyclooctane containing 1-8 substituent groups; the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together.
[0021] As an optimized technical proposal, the cycloalkane compound is selected from at least one kind of cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane and the adamantane.
[0022] In the present invention, no special limitation is set to the oxygen-containing atmosphere, thereby the oxygen-containing atmosphere is able to apply purity oxygen, enriched oxygen, air, or oxygen diluted by one or more kinds of non-reactive gases like nitrogen, helium, argon or carbon dioxide; oxygen dosage is reasonably selected according to the cycloketone compound, preferably, excess oxygen amount is selected relative to a cycloa1kane compound.
[0023] The temperature of the catalytic oxidation reaction is critical, as the reaction temperature is vary between 20-100°C; preferably, the reaction temperature is 30-50°C [0024] The benefits of the invention are as follows: (1) a composite catalyst system composed by the nitroxyl radical ligand and the lanthanum metal is applied in the present invention, and then aminoxyl radical is generated by a reaction of the nitroxyl radical ligand and the oxygen, thereby an intermediate is formed by combining with La3-, and then cooperated with the oxygen, the cycloalkane forms cycloalkyloxy lanthanum intermediate, thereby to react with the nitroxyl radical to form the cycloketone compound; thereby the conversion of the cycloalkane compound under moderate condition is improved, and then the selectivity of the ketone compound by ensuring a certain conversion of the cycloalkane compound; (2) the preparation process in the present invention has a moderate reaction condition, which reduces environment pollution, thereby operation performing in high temperature and high pressure as well as security problems are avoided; (3) the reaction process of the present invention is simple in manufacturing and strong in maneuverability, moreover, the catalyst is cheap to be obtained, and fixed catalyst is easy to be separated and recycled, which has a great industrial application prospect.
DETAILED DESCRIPTION OF THE INVENTION
[0025] Detailed descriptions of the present invention are her described below vyith reference to the embodiments and figures, however, the embodiments of the present invention are not limited to this.
[0026] Preparation method of nitroxyl radical hganti is listed as follows: 100mi: ethanol-water mixed solvent is prepared (3:2) is added into a three-necked bottle, and then about 5g of solid NH4C1 and 9g of 2,3-Dimethy1-2,3-dinitrobutane are weighed to add into the three-necked bottle, and then reacting for 30 min by using an ice water bath; about 20 g of Zn powder is slowly added into the three-necked bottle in 20h to be reacted for lh by using the ice water bath, and after reacting for 3h at room temperature, a suction filtration is performed, thereby 2,3-dimethy1-2,3-diaminobutane colorless solution is obtained after washed with water for four times; about 5g of arylformaldehyde is weighed to completely dissolve into the 2,3-dimethy1-2,3-diaminobutane colorless solution, and after reacting for 24h at the room temperature, solvent with white precipitate is processed with the suction filtration, and then the nitroxyl radical ligand is obtained after washing with small amount of absolute ethanol for several times.
[0027] Embodiment I [0028] The nitroxyl radical ligand(a)(0.4mmol), lanthanum nitrate hydrate(0.4mmol), 0 5mL of dilute sulfuric acid(0.1mol/L), 0.1683g of hexamethylene(2mmol), 20mL1,2-dichloroethane are orderly added into the three-necked bottle connected to a condenser pipe, a thermometer and an oxygen kit; under normal conditions, after stirring for 24h at 45°C, the temperature is cooled to the room temperature, and then GC internal standard method is adopted to detect and analyze, the conversion of the hexamethylene is 11.2%, and the selectivity of the cyclohexanone is 82.9%.
[002.9] Embodiment 2 [0030] The nitroxyl radical ligand(b)(0.4mmol), lanthanum nitrate hydrate(0.4mmol), 0.5mL of dilute sulfuric acid(0.1mol/L), 0 16/33g of h exam ethyl en e(2mm ol), 20m L1,2-dichloroethane are orderly added into the three-necked bottle connected to a condenser pipe, a thermometer and an oxygen kit; under normal conditions, after stirring for 24h at 45°C, the temperature is cooled to the room temperature, and then GC internal standard method is adopted to detect and analyze, the conversion of the hexamethylene is 15.6%, and the selectivity of the cyclohexanone is 85.9%.
[003 iI Embodiment 3 [0032] The nitroxyl radical ligand(c)(0.4mmol), lanthanum nitrate hydrate(0.4mmol), 0 5mL of dilute sulfuric acid(0.1mol/L), 0. /683(z of hexamethylene(2mmol), 20mL1,2-dichloroethane are orderly added into the three-necked bottle connected to a condenser pipe, a thermometer and an oxygen kit; under normal conditions, after stirring for 24h at 45°C, the temperature is cooled to the room temperature, and then GC internal standard method is adopted to detect and analyze, the conversion of the hexamethylene is 13.5%, and the selectivity of the cyclohexanone is 83.2%.
[0033] Embodiment 4 100341 The nitroxyl radical ligand(d)(0.4mmol), lanthanum nitrate hydrate(0.4mmol), 0 5mL of dilute sulfutic acid(0.1mol/L), 0 168.3g of hexamethylene(2mmol), 20mL1,2-dichloroethane are orderly added into the three-necked bottle connected to a condenser pipe, a thermometer and an oxygen kit; under normal conditions, after stirring for 24h at 45°C, the temperature is cooled to the room temperature, and then GC internal standard method is adopted to detect and analyze, the conversion of the hexamethylene is 12.3%, and the selectivity of the cyclohexanone is 81.3%.
[0035] Comparative example I [0036] Without adding catalytic system, the embodiment is preformed repeatedly, and after the detection and analysis, the hexamethylene almost does not react, thereby no targeted product is generated.
[0037] After comparison, the catalytic system is of vital importance in the reaction system of the present invention.
[0038] Comparative example 2 [0030] The nitroxyl radical ligand(d)(0.4mmol), 4,4,5,5-tetramethy1-2-imidazoline-lhydroxyethyl-oxide(NIT), the lanthanum nitrate hydrate(0.4mmol), 0.1683g of the hexamethylene(2mmol), 20mL 1,2-dichloroethane(DCE) are orderly added into the three-necked bottle connected to the condenser pipe, the thermometer and the oxygen kit; under normal conditions, after stirring for 24h at 45°C, the temperature is cooled to the room temperature, and then GC internal standard method is adopted to detect and analyze, the conversion of the hexamethylene is 3.3%, and the selectivity of the cyclohexanone is 70.5%.
Form 1 Catalyst Conversion /% Ketone selectivity/% Embodiment 1 (a) 11.2 82.9 Embodiment 2 (b) 15.6 85.9 Embodiment 3 (c) 13.5 83.2 Embodiment 4 (d) 12.3 81.3 Comparative example 1 / 0 0 Comparative example 2 NIT 3.3 70.5

Claims (9)

  1. CLAIMS1. A synthetic method of a cycloketone compound, wherein the synthetic method is listed as follows: under an oxygen-containing atmosphere, corresponding cycloketone compound is oxidized and synthesized from cycloalkane through a catalytic system, wherein the catalytic system comprises dilute sulfuric acid, organic nitroxyl radical precursor and lanthanum metal.
  2. 2. The synthetic method of a cycloketone compound defined in claim 1, wherein the organic nitroxyl radical precursor is selected from the following structures in formulas °),(1I) XIII) or (IV): (IV) wherein R in formula is selected from hydrogen atom, alkyl, cycloalkyl, aryl, heterocycle, hydroxy, nitryl or halogens.
  3. 3. The synthetic method of a cycloketone compound defined in claim 1, wherein the lanthanum metal is one of lanthanum nitrate hydrate, lanthanum chloride and lanthanum acetate.
  4. 4. The synthetic method of a cycloketone compound defined in claim 1, wherein a concentration of the dilute sulfuric acid is 0.05mol/L-3mol/L.
  5. 5. The synthetic method of a cycloketone compound defined in claim I., wherein nitroxyl radical ligand precursor is selected from at least one of the following formula (a)-(d): (a) (c) (d)
  6. 6. The synthetic method of a cycloketone compound defined in claim 1, wherein the cycloalkane is taken as material, wherein the cycloalkane is a saturated hydrocarbons compound and derivatives thereof contains one or more rings with 3-18 carbon atoms in molecular structure.
  7. 7. The synthetic method of a cycloketone compound defined in claim 1, wherein the cycloalkane is selected from at least one of cyclopentane compound, hexamethylene compound, cycloheptane compound, cyclooctane compound or adamantane, but not limited to the aforementioned ranges; the cyclopentane compound has 0-5 substituent groups, which can be either the cyclopentane or the cyclopentane containing 1-5 substituent groups, the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together; the hexamethylene compound has 0-6 substituent groups, which can be either the hexamethylene or the hexamethylene containing 1-6 substituent groups; the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together; the cycloheptane compound has 0-7 substituent groups, which can be either the cycloheptane or the cycloheptane containing 1-7 substituent groups; the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together; the cyclooctane compound has 0-8 substituent groups, which can be either the cyclooctane or the cyclooctane containing 1-8 substituent groups; the substituent groups are independently selected from the alkyl with 1-8 hydrogen atoms or carbon numbers, and when the substituent groups are able to be independently substituted when no less than 1, or at least two of the substituent groups form a ring together.
  8. 8. The synthetic method of a cycloketone compound defined in claim 1, wherein the cycloalkane compound is selected from at least one kind of cyclopentane, cyclohexane, methylcyclohexane, cycloheptane, cyclooctane and the adamantane.
  9. 9. The synthetic method of a cycloketone compound defined in claim 1, wherein the oxygen-containing atmosphere is able to apply purity oxygen, enriched oxygen, air, or oxygen diluted by one or more kinds of non-reactive gases like nitrogen, helium, argon or carbon dioxide.The synthetic method of a cycloketone compound defined in claim 1, wherein temperature of catalytic oxidation reaction is ranging from 20-100°C
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0878234A2 (en) * 1997-05-13 1998-11-18 Daicel Chemical Industries, Ltd. Oxygenation catalyst and process for producing a ketone using the same
WO2009058527A1 (en) * 2007-10-31 2009-05-07 Exxonmobil Chemical Patents Inc. Oxidation of hydrocarbons

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0878234A2 (en) * 1997-05-13 1998-11-18 Daicel Chemical Industries, Ltd. Oxygenation catalyst and process for producing a ketone using the same
WO2009058527A1 (en) * 2007-10-31 2009-05-07 Exxonmobil Chemical Patents Inc. Oxidation of hydrocarbons

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