CN102453004A - Synthetic method of epoxybutene - Google Patents

Abstract

The invention discloses a synthesis method of epoxybutene. The method comprises the steps of adding butadiene, a tetranitrogen metal ligand catalyst, hydrogen peroxide and a reaction medium into a closed reactor, reacting for 0.1-10 hours at a reaction temperature of-10-50 ℃ and under a pressure of normal pressure-3.0 MPa, and obtaining epoxybutene through conventional separation after the reaction is finished. The butadiene conversion rate reaches 80-90%, and the product selectivity is more than 99%.

Description

A kind of synthetic method of epoxybutene

technical field

The invention relates to a synthesis method of epoxybutene. Specifically, the invention uses butadiene as a reactant, hydrogen peroxide as an oxidant, and synthesizes epoxybutene under the action of a catalyst.

Background technique

Epoxybutene (Butadiene monoxide) is a new type of fine chemical raw material. Because epoxybutene has a unique molecular structure, that is, one molecule has both terminal double bonds and epoxy groups, so its chemical properties are very active. Its derivatives It is related to many fields, so it is called a new type of chemical intermediate, and important fine chemicals such as cyclopropylamine and tetrahydrofuran can be prepared from epoxybutene. Butadiene is rich in raw material resources, and its synthesis of epoxybutene has very important industrial value.

In the 1990s, Eastman Chemical Company successfully developed a new technology to produce epoxybutene by epoxidation of butadiene (Butadiene), which is to use molecular oxygen to carry out selective epoxy in the gas phase after ethylene oxidation to ethylene oxide. The only example of oxidization, the catalytic process is described in the patents US 4897498, 4950773, 5081096, the solid phase catalyst used in the reaction is very similar to the ethylene epoxidation Ag catalyst, the carrier is α-Al ₂ O ₃ with low surface area, the active group Divided into highly dispersed Ag clusters supported by the impregnation method, Cs, Ti, etc. were used as cocatalysts. Usually, besides butadiene and oxygen, the reaction raw materials also have 1,2-dichloroethane inhibitor and diluent gas. Chen Gexin et al also introduced similar work in the patent ZL 00132856.5. In short, it is generally necessary to add inhibitors and diluent gases in the reaction, which brings difficulties to the separation. The epoxidation of butadiene can be carried out by liquid-phase or heterogeneous methods. Most of the oxidants in the liquid phase method use H ₂ O ₂ , such as Romano Ugo; MasperoFedrico introduced Ti/Si molecular sieves as catalysts and H ₂ O ₂ as oxidants in the patent EO 190609, and carried out liquid phase epoxidation of diolefins to produce single epoxy. In Catalysis Letters, 2000, 66:175, Zhang Xiaoming and others also introduced the research of TS-1 catalyzed H ₂ O ₂ epoxidation of butadiene, and the reactivity needs to be improved.

Multidentate nitrogen complexes are effective catalysts for the oxidation of olefins. For example, in 2003, Stack et al. reported that [Mn ^II (R, R-mcp)(CF ₃ SO ₃ ) ₂ ] complexes catalyzed the epoxidation of electron-deficient alkenes. This catalytic system can rapidly oxidize a series of olefinic substrates to epoxy compounds using peracids as oxidants at room temperature (J.Am.Chem.Soc., 2003, 125, 5250-5251). Sun Wei and others have also done a lot of research (Organic Letters, 2009, 11, 3622-3625. Tetrahedron: Asymmetry, 2010, 21, 374-378, etc.).

Contents of the invention

The object of the present invention is to provide a kind of synthetic method of epoxybutene with good selectivity and simple method.

A method for synthesizing epoxybutene, which is characterized in that the method adds butadiene, catalyst, hydrogen peroxide and reaction medium into a closed reactor, and the reaction temperature is -10 to 50°C, and the pressure is normal pressure to 3.0MPa , react for 0.1 to 10 hours, and obtain epoxybutene through conventional separation after the reaction; the catalyst is tetranitrogen metal ligand.

The tetranitrogen ligand used in the present invention is composed of diamine and pyridine ring, wherein the diamine is selected from ethylenediamine, propylenediammonium, butylenediamine, cyclohexanediamine or phthalenediamine; the metal element is selected from manganese, titanium or iron.

The catalyst specifically used in the present invention is N,N'-(2-pyridylmethyl)ethyl-1,2-diamine and manganese trifluoromethanesulfonate complex (Mn(hep)(OTf) ₂ ), N, N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethyl-1,2-diamine complex with manganese trifluoromethanesulfonate (Mn(mep)(OTf) ₂ ), N , N′-Dimethyl-N, N′-bis(2-pyridylmethyl)ethyl-1,2-diamine complex with iron trifluoromethanesulfonate (Fe(mep)(OTf) ₂ ), N,N'-Dimethyl-N,N'-bis(2-pyridylmethyl)ethyl-1,2-diamine complex with titanium trifluoromethanesulfonate (Ti(mep)(OTf) ₂ ) , N, N'-dimethyl-N, N'-bis(2-pyridylmethyl)cyclohexyl-1,2-diamine complex with manganese trifluoromethanesulfonate (Mn(mcp)(OTf) ₂ ), N, N'-dimethyl-N, N'-bis(2-pyridylmethyl)cyclohexyl-1,2-diamine and iron trifluoromethanesulfonate complex (Fe(mcp)(OTf) ₂ ), N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)o-phenylenediamine complex with manganese trifluoromethanesulfonate (Mn(mpp)(OTf) ₂ ), N , N'-dimethyl-N,N'-bis(2-pyridylmethyl)ethyl-1,2-diamine complex with manganese acetate (Mn(mep)(CH ₃ CO ₂ ) ₂ ), N , N'-Dimethyl-N, N'-bis(2-pyridylmethyl)ethyl-1,2-diamine complex with manganese chloride (Mn(mep)Cl ₂ ) and N,N'- One of the complexes of dimethyl-N,N'-bis(2-pyridylmethyl)ethyl-1,2-diamine and ferric chloride (Fe(mep)Cl ₂ ).

The reaction medium of the present invention is acetonitrile, benzonitrile or dichloromethane.

The molar ratio of the tetranitrogen metal complex catalyst to butadiene in the present invention is 0.0001-0.02:1.

The molar ratio of hydrogen peroxide to butadiene in the present invention is 0.5-6:1.

The present invention has the advantages of rich butadiene resources as raw material, green oxidant as oxidant hydrogen peroxide, friendly to the environment, easy and convenient catalyst synthesis, high catalyst consumption, simple reaction system, mild reaction conditions, high butadiene conversion rate (up to 80-90 %), good product selectivity (preferably greater than 99%), can be separated by conventional methods after the reaction, and the raw materials can be reused again, thereby effectively utilizing resources, reducing operating costs, and having a good application prospect.

Detailed ways

In the present invention, the reactants and products are qualitatively analyzed by Aglient-GC/MS (6890/5973), and the capillary chromatographic column is: HP-5MS, TCD detector. Agilent-7890A gas chromatography was used for quantitative analysis, capillary column: SE-54 (50m×0.32mm×0.5μm), FID detector, temperature program, internal standard method for quantification, conversion and selectivity calculated by butadiene.

Example 1:

The molar ratio of butadiene, 4N-Fe catalyst (Fe(mep)Cl ₂ ), and hydrogen peroxide (28 to 30 wt%) is 1:0.01:6, butadiene, catalyst, hydrogen peroxide, and reaction medium acetonitrile are added to a closed container In the process, react at room temperature 25°C for 2 hours, take samples, dry, and analyze the reaction results by gas chromatography. The conversion rate of butadiene can reach 52%, and the selectivity: 89%. At this time, the product can be recovered by rectification.

Example 2:

The molar ratio of butadiene, 4N-Fe catalyst (Fe(mcp)(CF ₃ S0 ₃ ) ₂ ), hydrogen peroxide (28～30wt%) is 1:0.0005:2, butadiene, catalyst, hydrogen peroxide, reaction medium Dichloromethane was added in a closed container, reacted for 10 hours under normal pressure at -10°C, took a sample, dried, and analyzed the reaction results with gas chromatography. The conversion rate of butadiene can reach 75%, and the selectivity: 94%; The product was collected by distillation.

Example 3:

The molar ratio of butadiene, 4N-Mn catalyst (Mn(hcp)(CH ₃ CO ₂ ) ₂ ), hydrogen peroxide (28～30wt%) is 1:0.005:1, butadiene, catalyst, hydrogen peroxide, reaction medium Add acetonitrile into a closed container, react at 40°C and pressure 2MPa for 0.5 hours, take a sample, dry, and analyze the reaction result by gas chromatography. The conversion rate of butadiene can reach 64%, and the selectivity: 92%. At this time, the product can be collected by rectification .

Example 4:

The molar ratio of butadiene, 4N-Mn catalyst (Mn(mcp)(CF ₃ SO ₃ ) ₂ ), hydrogen peroxide (28～30wt%) is 1:0.0001:2, and butadiene, catalyst, hydrogen peroxide, and reaction medium Add acetonitrile into a closed container, react at -10°C and pressure 0.4MPa for 5 hours, take a sample, dry, and analyze the reaction result by gas chromatography. The conversion rate of butadiene can reach 55%, and the selectivity: 98%; at this time, it can be rectified Collect product.

Example 5:

The molar ratio of butadiene, 4N-Mn catalyst (Mn(mep)(CF ₃ SO ₃ ) ₂ ), hydrogen peroxide (28～30wt%) is 1:0.001:4, butadiene, catalyst, hydrogen peroxide, and reaction medium Add acetonitrile into a closed container, react at room temperature 25°C and normal pressure for 1 hour, take a sample, dry, and analyze the reaction result by gas chromatography. The conversion rate of butadiene can reach 84%, and the selectivity: 96%; at this time, it can be collected by rectification product. Embodiment 6: The molar ratio of butadiene, 4N-Mn catalyst (Mn(hep)(CF ₃ SO ₃ ) ₂ ), hydrogen peroxide (28～30wt%) is 1:0.005:6, butadiene, catalyst, Add hydrogen peroxide and benzonitrile as the reaction medium into a closed container, react for 10 hours at 0°C under normal pressure, take a sample, dry, and analyze the reaction result with gas chromatography. The conversion rate of butadiene can reach 80%, and the selectivity: 99%; at this time The product can be recovered by distillation.

Claims (6)

1. the compound method of an epoxy butylene; It is characterized in that this method joins divinyl, catalyzer, ydrogen peroxide 50 and reaction medium in the airtight reactor drum; In temperature of reaction-10～50 ℃; Pressure is normal pressure～3.0MPa, reacts 0.1～10 hour, and reaction finishes the back and obtains the epoxy butylene through the routine separation; Described catalyzer is four nitrogen metal ligands.

2. the method for claim 1 is characterized in that four nitrogen ligands are made up of diamines and pyridine ring, and wherein diamines is selected from quadrol, propane-diammonium, fourth two ammoniums, cyclohexanediamine or adjacent benzene two ammoniums; Metallic element is selected from manganese, titanium or iron.

3. according to claim 1 or claim 2 method is characterized in that catalyzer is N, N '-(2-picolyl) ethyl-1, and (Mn (hep) is (OTf) for 2-diamines and trifluoromethanesulfonic acid manganese complex ₂), N, N '-dimethyl--N, N '-two (2-picolyl) ethyl-1, (Mn (mep) is (OTf) for 2-diamines and trifluoromethanesulfonic acid manganese complex ₂), N, N '-dimethyl--N, N '-two (2-picolyl) ethyl-1, (Fe (mep) is (OTf) for 2-diamines and trifluoromethanesulfonic acid iron complex ₂), N, N '-dimethyl--N, N '-two (2-picolyl) ethyl-1, (Ti (mep) is (OTf) for 2-diamines and trifluoromethanesulfonic acid titanium complex ₂), N, N '-dimethyl--N, N '-two (2-picolyl) cyclohexyl-1, (Mn (mcp) is (OTf) for 2-diamines and trifluoromethanesulfonic acid manganese complex ₂), N, N '-dimethyl--N, N '-two (2-picolyl) cyclohexyl-1, (Fe (mcp) is (OTf) for 2-diamines and trifluoromethanesulfonic acid iron complex ₂), N, N '-dimethyl--N, (Mn (mpp) (OTf) for N '-two (2-picolyl) O-Phenylene Diamine and trifluoromethanesulfonic acid manganese complex ₂), N, N '-dimethyl--N, N '-two (2-picolyl) ethyl-1,2-diamines and manganous acetate title complex (Mn (mep) (CH ₃CO ₂) ₂), N, N '-dimethyl--N, N '-two (2-picolyl) ethyl-1,2-diamines and Manganous chloride tetrahydrate title complex (Mn (mep) Cl ₂) and N, N '-dimethyl--N, N '-two (2-picolyl) ethyl-1,2-diamines and iron(ic)chloride title complex (Fe (mep) Cl ₂) in a kind of.

4. the method for claim 1 is characterized in that reaction medium is acetonitrile, benzene nitrile or methylene dichloride.

5. the method for claim 1, the mol ratio that it is characterized in that four nitrogen metal complex catalysts and divinyl is 0.0001～0.02: 1.

6. the method for claim 1, the mol ratio that it is characterized in that ydrogen peroxide 50 and divinyl is 0.5～6: 1.