CN111039747B - Method for preparing norbornene compound containing trifluoromethyl and application thereof - Google Patents
Method for preparing norbornene compound containing trifluoromethyl and application thereof Download PDFInfo
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- CN111039747B CN111039747B CN201911355723.2A CN201911355723A CN111039747B CN 111039747 B CN111039747 B CN 111039747B CN 201911355723 A CN201911355723 A CN 201911355723A CN 111039747 B CN111039747 B CN 111039747B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/26—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton
- C07C17/272—Preparation of halogenated hydrocarbons by reactions involving an increase in the number of carbon atoms in the skeleton by addition reactions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Abstract
The invention relates to a method for preparing a norbornene compound containing trifluoromethyl and application thereof, belonging to the technical field of organic synthesis. Under the action of organic base, high valence copper trifluoromethyl compound is used as trifluoromethyl source to react with cyclopentadiene and dienophile to obtain trifluoromethyl substituted norbornene compound. The method has the advantages of simple and easily obtained reaction raw materials, catalyst, alkali and solvent, wide sources, convenient operation, no need of special storage and use conditions, safety, low cost, high yield, simple process, environmental protection and the like, and is expected to have important application value in the fields of pesticides, high polymer materials, dyes and the like.
Description
Technical Field
The invention relates to a method for preparing a norbornene compound containing trifluoromethyl and application thereof, belonging to the technical field of organic synthesis.
Background
Due to the unique properties of fluorine atoms, such as small atomic radius, super electronegativity, good lipid permeability and metabolic stability, and the like, the fluorine-containing compound has a plurality of unique biological and material activities, so the fluorine-containing compound has wide application in the aspects of pesticides, medicines, materials, and the like.
The trifluoromethyl gene has the characteristics of strong electronegativity, lipophilicity, firm C-F bond and the like, and CF is formed3The introduction into organic molecules can significantly alter the polarity, lipophilicity and metabolic stability of the compounds. The fluorine-containing compound has a plurality of unique biological pharmacology and material activity, so the fluorine-containing compound has wide application in the aspects of pesticides, medicines, materials and the like.
The reported trifluoromethylation reactions include nucleophilic trifluoromethylation, electrophilic trifluoromethylation and radical trifluoromethylation. However, most of these reactions require harsh reaction conditions or narrow substrate ranges, or poor product selectivity. For example, the more mature current method of trifluoromethylation is the use of TMSCF3Togni or Umemoto type reagents as a source of trifluoromethyl. Thus, how to efficiently and selectively introduce CF into a substrate3Is a problem which needs to be solved urgently.
Polymers of norbornene are used in a wide range of applications, for example for vibration resistance (railway, construction, industry), impact resistance (personal protective equipment, footwear fittings, bumpers) and for improving grip (toy tires, racing tires, transmission systems, copiers, fishing lines, etc.). The introduction of trifluoromethyl in norbornene can change the properties of norbornene, such as hydrophilicity/hydrophobicity and electrostatic property, and has latent value in improving performance defect in some current application and may be used in developing polynorbornene application field.
Disclosure of Invention
The invention aims to overcome the defects and provide the method for preparing the norbornene compound containing the trifluoromethyl and the application thereof.
The technical scheme of the invention is that under the action of organic base, a high valence copper trifluoromethyl compound is used as a trifluoromethyl source to react with cyclopentadiene and dienophile to obtain the trifluoromethyl substituted norbornene compound.
Further, in the reaction, the ratio of organic base: copper trifluoromethyl compound: cyclopentadiene: the mol ratio of the dienophile is 2-6: 1-3: 1: 1.
further, the reaction needs to be carried out in a solvent. The solvent is one or more of DMF, DMSO, DCE and xylene.
Further, the reaction temperature of the reaction is 90-130 ℃, and the reaction time is 3-20 hours; the reaction is carried out under an inert gas atmosphere.
In one embodiment of the invention, the method comprises the steps of reacting a mixed solution of a copper trifluoromethyl compound, cyclopentadiene, a dienophile and an organic base in an oil bath kettle at 90-130 ℃ for 3-20 hours under the protection of nitrogen; and cooling to room temperature after reaction, and obtaining a target product through filtration, washing, drying and chromatography.
Further, cooling the reaction system after the oil bath reaction to room temperature, adding dichloromethane for dilution, then taking an organic layer for washing by deionized water, and finally adding silica gel spin-dry column for chromatography to obtain the target product, namely the compound containing the trifluoromethyl.
Further, in the step, the adding amount of water is 5-10 times of the volume of the reaction system when water is added for dilution, and the adding amount of dichloromethane is equal to the volume of water.
Further, the chemical structural formula of the copper trifluoromethyl compound is shown as the following formula (I):
further, the organic base is Et3One or more of N, DBU, DABCO and DMDEA.
Further, the chemical structural formula of the dienophile is shown as a formula (II):
Further, in the step, when the dienophile is in a solid state, adding the copper trifluoromethyl compound, the alkali and the dienophile into a reaction tube, vacuumizing, filling nitrogen, and injecting the solvent and the cyclopentadiene by using an injector under the protection of the nitrogen.
Further, in the step, when the dienophile is in a liquid state, the copper trifluoromethyl compound and the organic base are added into a reaction tube, vacuum pumping is carried out, nitrogen gas is filled, and the dienophile, the cyclopentadiene and the solvent are injected by an injector under the protection of the nitrogen gas.
Further, the chemical structural formula of the norbornene compound containing trifluoromethyl substituent is shown as the formula (III):
The norbornene compound prepared by the method is applied to the fields of material and medicine synthesis.
The invention has the beneficial effects that: the raw materials, alkali and solvent used in the invention are all industrial commodities, are simple and easily available, have wide sources and low price, have very stable performance and do not need special storage conditions. The method has the characteristics of low cost, simple process, less pollution and the like, and is very expected to carry out large-scale industrial production.
Detailed Description
The present invention will be further described with reference to the following specific examples. The preparation method of the norbornene compound containing trifluoromethyl has the core strategy that a target product is prepared by one-step simultaneous trifluoromethylation and Diels-Alder reaction of a dienophile.
The invention will be further illustrated with reference to the following specific examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Simple replacement or improvement of the present invention by those skilled in the art is within the technical scheme of the present invention.
Example 1: a method for preparing a norbornene compound containing trifluoromethyl adopts the following process steps:
the copper trifluoromethyl compound 1(0.1mmol, 45mg) was placed in a 25mL reaction tube, evacuated, and purged with nitrogen (three times). DBU (0.2mmol, 20mg), cyclopentadiene (0.1mmol, 13.2mg), ethylene (3a,0.1mmol) and DCE were injected with a syringe under nitrogen: xylene-1: 1(1 mL). Stirring in 130 deg.C oil bath for 18h, cooling to room temperature, filtering, adding reaction solution and 20mL water to the extraction funnel, adding 25mL dichloromethane for extraction, and adding small amount of silica gel to the organic layer for spin-drying column chromatography to obtain product 4a (56% yield).
The reaction process of the above step is shown as the following formula (1):
the nuclear magnetic data for product 4a is as follows:
1H NMR(400MHz,CDCl3)δ6.05(s,2H),3.64–3.62(m,1H),2.84–2.82(m,1H),2.58–2.54(m,1H),1.75–1.56(m,2H),1.56–1.31(m,2H).13C NMR(101MHz,CDCl3)δ135.9,135.4,42.9,42.3,31.6,15.4.。
example 2 a process for the preparation of a trifluoromethyl group containing norbornene-type compound, using the following process steps:
the copper trifluoromethyl compound 1(0.1mmol, 45mg) was placed in a 25mL reaction tube, evacuated, and purged with nitrogen (three times). DBU (0.2mmol, 20mg), cyclopentadiene (0.1mmol, 13.2mg), propylene (3b,0.1mmol, 4.2mg) and DCE were injected with a syringe under nitrogen: xylene-1: 1(1 mL). Stirring in 130 deg.C oil bath for 18h, cooling to room temperature, filtering, adding reaction solution and 20mL water to the extraction funnel, adding 25mL dichloromethane for extraction, and adding small amount of silica gel to the organic layer for spin-drying column chromatography to obtain product 4b (62% yield).
The reaction process of the above step is shown as the following formula (2):
the nuclear magnetic data for product 4b is as follows:
1H NMR(400MHz,CDCl3)δ5.98(s,2H),3.54–3.52(m,1H),2.58–2.56(m,2H),1.58–1.54(m,1H),1.54–1.31(m,2H),0.88(s,3H).13C NMR(101MHz,CDCl3)δ135.9,132.9,49.5,46.7,46.5,29.1,21.6。
example 3: a method for preparing a norbornene compound containing trifluoromethyl adopts the following process steps:
copper trifluoromethyl compound 1(0.1mmol, 45mg) and polyvinyl alcohol (3c,0.1mmol, 4.5mg) were placed in a 25mL reaction tube, evacuated and purged with nitrogen (three times). DBU (0.2mmol, 20mg), cyclopentadiene (0.1mmol, 13.2mg) and DCE were injected with a syringe under nitrogen: xylene-1: 1(1 mL). Stirring in a 130 ℃ oil bath for 18h, cooling to room temperature, filtering, adding the reaction solution and 20mL of water into an extraction funnel, adding 25mL of dichloromethane for extraction, taking the organic layer, and adding a small amount of silica gel to spin-dry column chromatography to obtain a product 4c (yield 65%).
The reaction process of the above step is shown as the following formula (3):
the nuclear magnetic data for product 4c is as follows:
1H NMR(400MHz,CDCl3)δ6.24–6.21(m,1H),6.00–5.98(m,1H),4.77(s,1H),3.64–3.54(m,2H),2.58–2.56(m,1H),2.19–2.16(m,1H),1.75–1.50(m,2H).13C NMR(101MHz,CDCl3)δ135.9,133.1,129.2,132.9,56.5,50.0,47.4,44.5,25.4.
example 4: a method for preparing a norbornene compound containing trifluoromethyl adopts the following process steps:
the copper trifluoromethyl compound 1(0.1mmol, 45mg) was placed in a 25mL reaction tube, evacuated, and purged with nitrogen (three times). DBU (0.2mmol, 20mg), cyclopentadiene (0.1mmol, 13.2mg), acrylonitrile (3d,0.1mmol, 5.3mg) and DCE were injected with a syringe under nitrogen: xylene-1: 1(1 mL). Stirring in 130 deg.C oil bath for 18h, cooling to room temperature, filtering, adding reaction solution and 20mL water to extraction funnel, adding 25mL dichloromethane for extraction, and adding small amount of silica gel to organic layer for spin-drying column chromatography to obtain white solid 4d (yield 45%).
The reaction process of the above step is shown as the following formula (4):
the nuclear magnetic data for product 4d are as follows:
1H NMR(400MHz,CDCl3)δ6.24–6.21(m,1H),6.00–5.98(m,1H),3.65–3.56(m,1H),2.58–2.56(m,1H),2.45–2.44(m,1H),2.22–2.19(m,1H),1.75–1.50(m,2H).13C NMR(101MHz,CDCl3)δ138.4,135.9,132.1,50.2,47.2,39.7,28.3,6.6.
example 5: a method for preparing a norbornene compound containing trifluoromethyl adopts the following process steps:
the copper trifluoromethyl compound 1(0.1mmol, 45mg) was placed in a 25mL reaction tube, evacuated, and purged with nitrogen (three times). DBU (0.2mmol, 20mg), cyclopentadiene (0.1mmol, 13.2mg), propylene (3b,0.1mmol, 4.2mg) and DCE were injected with a syringe under nitrogen: xylene-1: 1(1 mL). Stirring in 130 deg.C oil bath for 18h, cooling to room temperature, filtering, adding reaction solution and 20mL water to the extraction funnel, adding 25mL dichloromethane for extraction, and adding small amount of silica gel to the organic layer for spin-drying column chromatography to obtain product 4e (yield 72%).
The reaction process of the above step is shown as the following formula (2):
Claims (4)
1. a method for preparing a norbornene compound containing a trifluoromethyl group, which is characterized by comprising the following steps: under the action of organic base, taking a high-valence copper trifluoromethyl compound as a trifluoromethyl source, and reacting the trifluoromethyl source with cyclopentadiene and dienophile to obtain a trifluoromethyl-substituted norbornene compound;
the chemical structural formula of the copper trifluoromethyl compound is shown as the following formula (I):
(I)L-CuIII(CF3)3，
The chemical structural formula of the dienophile is shown as the formula (II):
the chemical structural formula of the trifluoromethyl-substituted norbornene compound is shown as the formula (III):
in the reaction, the organic base: copper trifluoromethyl compound: cyclopentadiene: the mol ratio of the dienophile is 2-6: 1-3: 1: 1;
the reaction temperature is 90-130 ℃, and the reaction time is 3-20 h; the reaction is carried out under an inert gas atmosphere.
2. The method for producing a trifluoromethyl group-containing norbornene-type compound according to claim 1, wherein: the organic base is Et3One or more of N, DBU, DABCO and DMDEA.
3. The method for producing a trifluoromethyl group-containing norbornene-type compound according to claim 1, wherein: the reaction needs to be carried out in a solvent.
4. The method for producing a trifluoromethyl group-containing norbornene-type compound according to claim 3, wherein: the solvent is one or more of DMF, DMSO, DCE and xylene.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005330234A (en) * | 2004-05-20 | 2005-12-02 | Mitsubishi Chemicals Corp | (meth)acrylic ester and method for producing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2005330234A (en) * | 2004-05-20 | 2005-12-02 | Mitsubishi Chemicals Corp | (meth)acrylic ester and method for producing the same |
Non-Patent Citations (5)
| Title |
|---|
| Approaches to highly polar polymers with low glass transition temperatures. 1. Fluorinated polymers via a combination of ring-opening metathesis polymerisation and hydrogenation;W. James Feast, et al.;《Polymer》;20030716;第44卷(第19期);6111-6121 * |
| Radical C-H Bond Trifluoromethylation of Alkenes by High-Valent Copper(III) Trifluoromethyl Compounds;Hao-Ran Zhang, et al.;《Adv. Synth. Catal.》;20191112;第361卷(第23期);5305-5310 * |
| W. James Feast, et al..Approaches to highly polar polymers with low glass transition temperatures. 1. Fluorinated polymers via a combination of ring-opening metathesis polymerisation and hydrogenation.《Polymer》.2003,第44卷(第19期),6111-6121. * |
| 三氟甲基化合物的合成;陈献等;《化工新型材料》;20051025(第10期);63-66 * |
| 降冰片烯类化合物的合成及其表征研究;刘保霞等;《邢台职业技术学院学报》;20070330(第01期);46-47,76 * |
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