阅读说明：本技术 卟啉钴(ii)/铜(ii)盐协同催化氧化环烷烃的方法 (Cobalt Porphyrin (II)/copper (II) salt concerted catalysis oxidation cycloalkane method ) 是由 沈海民 宁磊 佘远斌 于 2019-08-28 设计创作，主要内容包括：一种卟啉钴(II)/铜(II)盐协同催化氧化环烷烃的方法,所述方法包括：将卟啉钴(II)和铜(II)盐分散于环烷烃中,密封反应体系,搅拌下升温至100～130℃,通入氧气至0.2～3MPa,保持设定的温度和氧气压力,搅拌反应3～24h,之后反应液经后处理,得到产物环烷醇和环烷酮；本发明所述方法,环烷醇和环烷酮选择性高,有效抑制了脂肪族二酸的生成；助催化剂廉价易得,环烷醇和环烷酮合成成本低；脂肪族二酸选择性低,也有利于环烷烃氧化过程的连续化和产品的分离；具有解决工业上环烷烃催化氧化过程中,环烷醇和环烷酮易于深度氧化生成脂肪族二酸的潜力；本发明是一种高效、可行的环烷烃选择性催化氧化新方法。(A kind of method of Cobalt Porphyrin (II)/copper (II) salt concerted catalysis oxidation cycloalkane, the described method includes: dispersing Cobalt Porphyrin (II) and copper (II) salt in cycloalkane, seal reaction system, 100~130 DEG C are warming up under stirring, oxygen is passed through to 0.2~3MPa, keeps the temperature and oxygen pressure of setting, it is stirred to react 3~for 24 hours, reaction solution is post-treated later, obtains product cyclic alkanol and cyclanone；The method of the invention, cyclic alkanol and cyclanone selectivity are high, effectively inhibit the generation of aliphatic diacid；Co-catalyst is cheap and easy to get, and cyclic alkanol and cyclanone synthesis cost are low；Aliphatic diacid is selectively low, is also beneficial to the serialization of cycloalkanes oxidation process and the separation of product；With in the industrial cycloalkane catalytic oxidation process of solution, cyclic alkanol and cyclanone are easy to the potentiality that deep oxidation generates aliphatic diacid；The present invention is a kind of efficient, feasible cycloalkane selective catalytic oxidation new method.)

1. a kind of Cobalt Porphyrin (II)/copper (II) salt concerted catalysis oxidation cycloalkane method, which is characterized in that the method packet It includes:

It disperses Cobalt Porphyrin (II) and copper (II) salt in cycloalkane, seals reaction system, 100~130 DEG C are warming up under stirring, Oxygen is passed through to 0.2~3MPa, keeps the temperature and oxygen pressure of setting, it is stirred to react 3~for 24 hours, reaction solution is after later Reason, obtains product cyclic alkanol and cyclanone；

The ratio between amount of substance of the Cobalt Porphyrin (II) and cycloalkane is 1:1000000~500；

The ratio between amount of substance of copper (II) salt and cycloalkane is 1:2000~20；

The cycloalkane are as follows: one or more of pentamethylene, hexamethylene, cycloheptane, cyclooctane, cyclononane, cyclodecane The mixture of arbitrary proportion；

Copper (II) salt be copper acetate and its hydrate, copper sulphate and its hydrate, copper chloride and its hydrate, copper nitrate and One or more of its hydrate, copper carbonate and its hydrate, acetylacetone copper and its hydrate arbitrary proportion it is mixed Close object；

The Cobalt Porphyrin (II) is at least one of compound shown in formula (I):

In formula (I), R₁、R₂、R₃、R₄、R₅It is respectively independent are as follows: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, phenyl, 1- naphthalene, 2- naphthalene, methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, ethylamino, dimethylamino, 1- hydroxyethyl, Nitro, cyano, carboxyl, benzyl, fluorine, chlorine, bromine or iodine.

2. Cobalt Porphyrin (II) as described in claim 1/copper (II) salt concerted catalysis oxidation cycloalkane method, which is characterized in that The ratio between amount of substance of the Cobalt Porphyrin (II) and cycloalkane is 1:100000~1000.

3. Cobalt Porphyrin (II) as described in claim 1/copper (II) salt concerted catalysis oxidation cycloalkane method, which is characterized in that The ratio between amount of substance of copper (II) salt and cycloalkane is 1:1000~100.

4. Cobalt Porphyrin (II) as described in claim 1/copper (II) salt concerted catalysis oxidation cycloalkane method, which is characterized in that The rate of the stirring is 100~1500rpm.

5. Cobalt Porphyrin (II) as described in claim 1/copper (II) salt concerted catalysis oxidation cycloalkane method, which is characterized in that Copper (II) salt is copper acetate or acetylacetone copper.

6. Cobalt Porphyrin (II) as described in claim 1/copper (II) salt concerted catalysis oxidation cycloalkane method, which is characterized in that The Cobalt Porphyrin (II) are as follows: 5,10,15,20- tetra- (4- chlorphenyl) Cobalt Porphyrin (II), 5,10,15,20- tetra- (2- chlorphenyl) porphin Quinoline cobalt (II), 5,10,15,20- tetra- (3- chlorphenyl) Cobalt Porphyrin (II), 5,10,15,20- tetra- (2,6- dichlorophenyl) Cobalt Porphyrin (II), 5,10,15,20- tetra- (2,4 dichloro benzene base) Cobalt Porphyrin (II) or 5,10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) Cobalt Porphyrin (II).

Technical field

The present invention relates to a kind of Cobalt Porphyrin (II)/oxygen selectivity oxidized cycloalkane of copper (II) salt concerted catalysis molecule to prepare ring The new method of alkanol and cyclanone belongs to organic catalysis and Minute Organic Synthesis field.

Background technique

Cycloalkane catalysis oxidation is an important chemical industry conversion process, and oxidation product cyclic alkanol, cyclanone are not only Important organic solvent, is also important fine-chemical intermediate, is widely used in the fine chemical products such as pesticide, medicine, dyestuff Synthesis (WO 2019046316；WO 2019030294；WO 2019069911；CN 108864082；CN 109180556； Journal of Medicinal Chemistry 2019,62:1837-1858；Russian Journal of General Chemistry 2018,88:2646-2652).In addition to this, cyclic alkanol and cyclanone can also further aoxidize preparation fat Race's diacid, aliphatic diacid are the important as precursors for preparing various high molecular materials, such as the primary product ring of catalytic oxidation of cyclohexane Hexanol and cyclohexanone further aoxidize the important as precursors adipic acid of available production nylon -66 and nylon-6, and the market demand is non- Often big (Applied Catalysis A, General 2019,575:120-131；Chemical Engineering Science 2019,203:163-172；Applied Catalysis A, General 2018,554:71-79； Industrial&Engineering Chemistry Research 2017,56:15030-15037).Currently, industrial ring Catalytic oxidation alkane is mainly using homogeneous cobalt (II) salt or manganese (II) salt as catalyst, and molecular oxygen or air are oxidant, 130 ~160 DEG C, (Applied the Catalysis A, General 2019,575:120- realized under 0.80~3.0MPa pressure 131；Science 2014,346:1495-1498).Due to reaction temperature height, the cyclic alkanol and cyclanone of generation are easy to depth oxygen Metaplasia is at aliphatic diacid.Although cyclic alkanol and cyclanone are the raw material for preparing aliphatic diacid, cyclic alkanol and cyclanone In production process, leading to the problem of for aliphatic diacid is to need to avoid.The generation of aliphatic diacid can block cycloalkane The pipeline of catalytic oxidation process, is unfavorable for continuous production.Therefore, selective cycloalkane catalysis oxidation new method is developed, is being protected Under the premise of demonstrate,proving cycloalkanes rate, the selectivity of cyclic alkanol and cyclanone is improved to the maximum extent, reduces and avoid aliphatic The generation of diacid is the urgent need of cycloalkane catalysis oxidation industry, has great production application value, it may have important Theoretical research value.

Model compound of the metalloporphyrin as cytochrome P-450 is widely used in all kinds of organic syntheses of bionic catalysis Reaction, especially oxidation reaction (ChemSusChem 2019,12:684-691；Polyhedron 2019,163:144-152； Journal of Catalysis 2019,369:133-142).Metalloporphyrin has the molecular structure of almost plane, makes to have The metal center of catalytic activity can be exposed in catalyst system to the maximum extent and play a role, the 1/1000000 of amount of substrate ~1/100000 can show excellent catalytic activity, can significantly reduce the cost of cycloalkane catalysis oxidation, be cycloalkanes One of the preferred catalyst of hydrocarbon catalysis oxidation (ChemSusChem 2019,12:684-691；Polyhedron 2019,163: 144-152；Journal of Catalysis 2019,369:133-142).Although metalloporphyrin has catalysis as catalyst Agent dosage is few, high catalytic efficiency, structure are easy to adjust, bio-compatibility is good, the advantages such as environmentally protective, but in catalytic molecular oxygen During oxidation cycloalkane prepares cyclic alkanol and cyclanone, still fail the generation for reducing and avoiding aliphatic diacid.In order to reduce Or avoid the generation of aliphatic diacid in cycloalkane catalytic oxidation process, the present invention with porphyrin Co (II) for major catalyst, Zn (II) salt is that co-catalyst catalytic molecular oxygen aoxidizes cycloalkane in the absence of a solvent, not only significantly improves cyclic alkanol and ring The conversion ratio of the selectivity of alkanone, cycloalkane also increases, and realizes the inhibition of aliphatic diacid during cycloalkanes oxidation. Therefore, for the present invention with porphyrin Co (II) for major catalyst, Zn (II) salt is co-catalyst catalytic molecular oxygen in solvent-free condition Lower oxidation cycloalkane has and solves in industrial cycloalkane catalytic oxidation process, and cyclic alkanol and cyclanone are easy to deep oxidation life At the potentiality of aliphatic diacid, there is important industrial application value and theoretical research value, other catalytic oxidation systems are selected The raising of selecting property also has certain reference value.

Summary of the invention

The purpose of the present invention is to provide a kind of Cobalt Porphyrin (II)/oxygen selectivity oxidized rings of copper (II) salt concerted catalysis molecule Alkane prepares the new method of cyclic alkanol and cyclanone.

Technical scheme is as follows:

A kind of method of Cobalt Porphyrin (II)/copper (II) salt concerted catalysis oxidation cycloalkane, which comprises

It disperses Cobalt Porphyrin (II) and copper (II) salt in cycloalkane, seals reaction system, it is warming up to 100 under stirring~ 130 DEG C (preferably 110~120 DEG C), be passed through oxygen to 0.2~3MPa (preferably 0.6~1.2MPa), keep setting temperature and Oxygen pressure is stirred to react 3~for 24 hours (preferably 8~16h), and reaction solution is post-treated later, obtains product cyclic alkanol and cycloalkanes Ketone；

In the method for the invention, cycloalkane is reaction raw materials, and Cobalt Porphyrin (II) is major catalyst, and copper (II) salt is to help to urge Agent, molecular oxygen are oxidant；

The ratio between amount of substance of the Cobalt Porphyrin (II) and cycloalkane is 1:1000000~500, preferably 1:100000~ 1000；

The ratio between amount of substance of copper (II) salt and cycloalkane is 1:2000~20, preferably 1:1000~100；

The rate of the stirring is 100~1500rpm, preferably 600~1200rpm；

The method of the post-processing are as follows: after reaction, triphenylphosphine (PPh is added into reaction solution₃, dosage is cycloalkanes The 2.5~25% of the amount of hydrocarbon materials), the peroxide that stirring 30min reduction generates under room temperature (20~30 DEG C), crude product is through steaming It evaporates, rectification under vacuum and recrystallization can obtain oxidation product；

Analysis method of the present invention to reaction result are as follows: after reaction, the mistake that reaction solution is generated through triphenylphosphine reduction Oxide, then sampling is analyzed, and is diluted by solvent of acetone, using toluene as internal standard, carries out gas chromatographic analysis, meter The conversion ratio of cycloalkane is calculated, the selectivity of cyclic alkanol, cyclanone and peroxide carries out liquid chromatogram using benzoic acid as internal standard Analysis, calculates the selectivity of aliphatic diacid；

In the present invention, the cycloalkane is for example are as follows: pentamethylene, hexamethylene, cycloheptane, cyclooctane, cyclononane, in cyclodecane One or more kinds of arbitrary proportions mixture；

Copper (II) salt is copper acetate and its hydrate, copper sulphate and its hydrate, copper chloride and its hydrate, nitric acid One or more of copper and its hydrate, copper carbonate and its hydrate, acetylacetone copper and its hydrate arbitrary proportion Mixture, preferably copper acetate or acetylacetone copper；

The Cobalt Porphyrin (II) is at least one of compound shown in formula (I), specific preferred: 5,10,15,20- tetra- (4- Chlorphenyl) Cobalt Porphyrin (II), 5,10,15,20- tetra- (2- chlorphenyl) Cobalt Porphyrin (II), 5,10,15,20- tetra- (3- chlorphenyl) Cobalt Porphyrin (II), 5,10,15,20- tetra- (2,6- dichlorophenyl) Cobalt Porphyrin (II), 5,10,15,20- tetra- (2,4 dichloro benzene base) Cobalt Porphyrin (II) or 5,10,15,20- tetra- (2,3,4,5,6- pentafluorophenyl group) Cobalt Porphyrin (II)；

In formula (I), R₁、R₂、R₃、R₄、R₅It is respectively independent are as follows: hydrogen, methyl, ethyl, propyl, butyl, isopropyl, tert-butyl, Phenyl, 1- naphthalene, 2- naphthalene, methoxyl group, ethyoxyl, hydroxyl, sulfydryl, amino, methylamino, ethylamino, dimethylamino, 1- hydroxyl Ethyl, nitro, cyano, carboxyl, benzyl, fluorine, chlorine, bromine or iodine.

The beneficial effects are mainly reflected as follows:

Cobalt Porphyrin (II) of the present invention/oxygen selectivity oxidized cycloalkane of copper (II) salt concerted catalysis molecule prepares cyclic alkanol and ring The method of alkanone, cyclic alkanol and cyclanone selectivity are high, effectively inhibit the generation of aliphatic diacid；Co-catalyst is inexpensively easy , cyclic alkanol and cyclanone synthesis cost are low；Aliphatic diacid is selectively low, is also beneficial to the serialization of cycloalkanes oxidation process With the separation of product；With in the industrial cycloalkane catalytic oxidation process of solution, cyclic alkanol and cyclanone are easy to deep oxidation life At the potentiality of aliphatic diacid.The present invention is a kind of efficient, feasible cycloalkane selective catalytic oxidation new method.

Specific embodiment

Invention is further explained combined with specific embodiments below, but protection scope of the present invention is not limited in This.

Metalloporphyrin used in the present invention refers to Journal of the American Chemical Society 2017,139:18590-18597；Journal of the American Chemical Society 2018,140:6383- 6390 synthesis.Agents useful for same is that commercially available analysis is pure.