CN110128438A - A kind of method and its application of photocatalysis biology base furans Diels-Alder reaction - Google Patents
A kind of method and its application of photocatalysis biology base furans Diels-Alder reaction Download PDFInfo
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- CN110128438A CN110128438A CN201910455668.8A CN201910455668A CN110128438A CN 110128438 A CN110128438 A CN 110128438A CN 201910455668 A CN201910455668 A CN 201910455668A CN 110128438 A CN110128438 A CN 110128438A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/12—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains three hetero rings
- C07D493/18—Bridged systems
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- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
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Abstract
The invention discloses a kind of methods of photocatalysis biology base furans Diels-Alder reaction, it is reacted it is characterized by: conjugated diene body biology base furfuran compound 1 carries out Diels-Alder with dienophile compound 2, generates 7- oxabicyclo [2.2.1] -5- heptene molecular skeleton compound.The present invention solves traditional D-A reaction and carries out under high temperature heating conditions, and reaction needs solvent, and process energy consumption is high and environment is unfriendly, and efficiency of pcr product is low, the stereoselectivity difference problem of product.
Description
Technical field
The invention belongs to biomass field of fine chemical, and in particular to a kind of photocatalysis biology base furans Diels-Alder
The method and its application of reaction.
Background technique
Diels-Alder (D-A) reaction is the important method for efficiently synthesizing the compound of molecular skeleton containing polycyclic system, is passed through
The divinyl macromer of one electron rich and [4+2] cycloaddition reaction is carried out with the dienophile of electron deficient form stable hexatomic ring chemical combination
Object, the concerted reaction completed for a step.Furan nucleus participate in D-A reaction can single step oxa- ring is introduced directly into molecule, easy shape
At the hexatomic ring of the key containing bridging oxygen, there is unique advantage in building Oxygenic heterocyclic compounds, and the bridging oxygen key generated is in Louis
It is easy open loop in the presence of this acid, and hexa-atomic full carbon aromatic rings can be converted five yuan of oxygen-containing furan nucleus to by aromatisation, therefore
The achievement attracted attention is achieved in terms of the polycyclic compound of composite structure complexity.
Currently, tradition D-A reaction carries out under high temperature heating conditions, reaction needs solvent, and process consumes energy high and environment not
Close friend, efficiency of pcr product is low, and the stereoselectivity of product is poor.Compared to traditional thermal chemical reaction, photochemical reaction is for realizing
Simple building block single step constructs highly complex organic molecule, makees in the transition metal complexes such as metal iridium (Ir) or ruthenium (Ru)
After being used widely in photochemical reaction for catalyst, because its mild reaction condition and high transformation efficiency are considered real
The effective way of existing green syt efficiently synthesizes aspect in the complicated polycyclic carbon skeleton of design and shows great potential, naturally producing
There is very high value during object is fully synthetic.
Photocatalysis D-A reaction can carry out at room temperature, and the cis- anti-structure that product is realized in photoisomerization reaction can also occur
Type conversion, provides a kind of new way of unique target compound of composite structure.
Biology base furans is from a wealth of sources, Typical Representative of the furan nucleus in structure as five-ring heterocycles, has aromatic ring property,
The electrophilic substitution reactions such as halogenation, nitrification, cyclisation can occur.The biology bases such as 2,5- dimethyl furan, furfural, 5 hydroxymethyl furfural
Furan compound contains complicated ring system structure, can be used as the molecular basis of Various Complex molecular structure.It is organic from photocatalysis
Chemical terms incision, to promote the derivatization of biology base Furan Molecules to produce the exploitation of biomass chemicals, biomass chemical industry
The development of industry and the efficient research on utilization of the high level of biomass resource have significant application value.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is using visible light as new clean energy resource supply mode, Ru
(II) transition metal complex Ru (bpy)3 2+For photochemical catalyst, a kind of photocatalysis biology base furans Diels-Alder reaction is provided
Method, reaction condition is mild, process green, reaction and post-processing purification process it is simple.
It is a further object of the present invention to provide the applications of the above method.
To achieve the goals above, the invention provides the following technical scheme:
A kind of method of photocatalysis biology base furans Diels-Alder reaction, by conjugated diene body biology base furans
It closes object 1 to react with the progress of dienophile compound 2 Diels-Alder, generates 7- oxabicyclo [2.2.1] -5- heptene molecule bone
Frame compound 3.
In room temperature, it is seen that under light irradiation, Ru (bpy)3 2+Under conditions of catalyst, reaction equation is
In above-mentioned reaction, the electron-withdrawing substituent GDE of the compound 1 is electron-donating group H and/or CH3, described
The electron-withdrawing substituent EWG of compound 2 is COR and/or CO2R。
In above-mentioned reaction, include the following steps:
(1) under the radiation of visible light for containing 365nm wavelength with specific wavelength, ruthenium complex Ru (bpy)3 2+Absorb light
One in wave electronically forms+divalent radical cation Ru (bpy)3 2+, the metal complex and dienophile maleic acid
After the LUMO rail effect of acid anhydride, an electronics in LUMO track is excited to give metal complex, metal complex is reduced to+
1 valence metal complex Ru (bpy)3 1+, while maleic anhydride conversion becomes dienophile radical cation；Then in O2Work
Under, by the metal complex Ru (bpy) of+1 valence3 1+Oxidation obtains+divalent metal complex Ru (bpy)3 2+, match the metal
It closes object and enters next illumination oxidation cycle；
(2) the LUMO track of maleic anhydride dienophile radical cation and the HOMO track of diene body furans are mutually tied
It closes, [4+2] pericyclic reaction occurs, i.e., reacts to form 7- oxabicyclo [2.2.1] -5- heptene molecular skeleton in Diels-Alder
Compound, meanwhile, free radical electronics is transmitted, and bridged ring radical cation midbody compound 3 is obtained·+；
(3) by base cation midbody compound 3·+It is anti-that free-radical oxidation is carried out for dienophile raw material maleic anhydride
It answers, obtains an electronics, transform into target neutral molecule 7- oxabicyclo [2.2.1] -5- heptene molecular skeleton compound 3.
The present invention provides a kind of application of photocatalysis biology base furans Diels-Alder reaction, specific reaction equations are as follows:
In above-mentioned application, include the following steps:
(1) according to molal weight ratio by furans: maleic anhydride: (2,2'- bipyridyl) ruthenous chloride is 1:1.5:0.005
The round-bottomed flask that stirrer is housed is added, is passed through oxygen after degassing, is placed in high-pressure sodium lamp in room temperature reaction；
(2) in above-mentioned reaction, reaction process is monitored by chromatographic sheet (TLC)；
(3) it is monitored by TLC and stops reacting after reaction raw materials furans completely disappears, reaction solution extracts through ethyl acetate, is full
It is dry with anhydrous sodium sulfate with the organic matter extraction phase obtained after brine It, concentration, using filter, concentration, recrystallization,
Up to compound 6.
The beneficial effects of the present invention are:
1, using light as new clean energy resource supply mode, reaction condition is mild for light-catalyzed reaction, can carry out at room temperature, instead
Condition is answered to need simple.
2, reaction process environmental protection, green energy conservation no longer need to add other organic solvents, and post-reaction treatment is washed without soda acid
It washs.
3, emission is few, without secondary pollution, and post-processing and purifying are simple.
Detailed description of the invention
Fig. 1 is chemical principle figure provided by the invention；
Fig. 2 is second embodiment intermediate molecule1H NMR(300MHz,CDCl3) spectrogram；
Fig. 3 is second embodiment intermediate molecule13C NMR(75MHz,CDCl3) spectrogram；
Fig. 4 is the detailed spectrogram of compound 6 provided by the invention.
Specific embodiment
Embodiment 1
On the one hand, a kind of method for present embodiments providing photocatalysis biology base furans Diels-Alder reaction, will be conjugated
Divinyl macromer biology base furfuran compound 1 carries out Diels-Alder with dienophile compound 2 and reacts, and generates 7- oxabicyclo
[2.2.1] -5- heptene molecular skeleton compound 3.
In room temperature, it is seen that under light irradiation, Ru (bpy)3 2+Under conditions of catalyst, reaction equation is
In above-mentioned reaction, the electron-withdrawing substituent GDE of the compound 1 is electron-donating group H and/or CH3, described
The electron-withdrawing substituent EWG of compound 2 is COR and/or CO2R。
In above-mentioned reaction, as shown in Figure 1, including the following steps:
(1) under the radiation of visible light for containing 365nm wavelength with specific wavelength, ruthenium complex Ru (bpy)3 2+Absorb light
One in wave electronically forms+divalent radical cation Ru (bpy)3 2+, the metal complex and dienophile maleic acid
After the LUMO rail effect of acid anhydride, an electronics in LUMO track is excited to give metal complex, metal complex is reduced to+
1 valence metal complex Ru (bpy)3 1+, while maleic anhydride conversion becomes dienophile radical cation；Then in O2Work
Under, by the metal complex Ru (bpy) of+1 valence3 1+Oxidation obtains+divalent metal complex Ru (bpy)3 2+, match the metal
It closes object and enters next illumination oxidation cycle；
(2) the LUMO track of maleic anhydride dienophile radical cation and the HOMO track of diene body furans are mutually tied
It closes, [4+2] pericyclic reaction occurs, i.e., reacts to form 7- oxabicyclo [2.2.1] -5- heptene molecular skeleton in Diels-Alder
Compound, meanwhile, free radical electronics is transmitted, and bridged ring radical cation midbody compound 3 is obtained·+；
(3) by base cation midbody compound 3·+It is anti-that free-radical oxidation is carried out for dienophile raw material maleic anhydride
It answers, obtains an electronics, transform into target neutral molecule 7- oxabicyclo [2.2.1] -5- heptene molecular skeleton compound 3.
On the other hand, a kind of application of photocatalysis biology base furans Diels-Alder reaction is present embodiments provided, specifically
Reaction equation are as follows:
In above-mentioned application, include the following steps:
(1) according to molal weight ratio by furans: maleic anhydride: (2,2'- bipyridyl) ruthenous chloride is 1:1.5:0.005
The round-bottomed flask that stirrer is housed is added, is passed through oxygen after degassing, is placed in high-pressure sodium lamp in room temperature reaction；
(2) in above-mentioned reaction, reaction process is monitored by chromatographic sheet (TLC)；
(3) it is monitored by TLC and stops reacting after reaction raw materials furans completely disappears, reaction solution extracts through ethyl acetate, is full
It is dry with anhydrous sodium sulfate with the organic matter extraction phase obtained after brine It, concentration, using filter, concentration, recrystallization,
Up to 7- oxygen two rings [2.2.1] hexane derivative compound 6.
Embodiment 2
As shown in connection with fig. 4, compound 6 is pre-polymerization structural unit, the drug molecule weight of macromolecule polymeric material to the present embodiment
Intermediate is wanted, a kind of application of photocatalysis biology base furans Diels-Alder reaction, including following mole are present embodiments provided
Quality:
Furans 4 (34.7g, 0.509mol), maleic anhydride 5 (5.0g, 0.051mol), (2,2'- bipyridyl) ruthenous chloride
[Ru(bpy)3Cl2, 30mmg] and the round-bottomed flask that stirrer is housed is added, it is passed through oxygen after degassing, is placed in high-pressure sodium lamp in room temperature
Reaction.
Reaction process is monitored by chromatographic sheet during reaction, after completely disappearing by TLC monitoring reaction raw materials furans 4
Stop reaction,
The organic solvent extraction phase that reaction solution is extracted through ethyl acetate, obtained after saturated common salt water washing, uses anhydrous slufuric acid
Sodium is dry, using filter, concentration, recrystallization to get compound 6, yield 65% (0.0335.5g).
6 Structural Identification of compound
In conjunction with as Figure 2-3, experimental result is
TLC (EtOAc/hexane=1/5): Rf=0.25 (UV)；
1H NMR(300MHz,CDCl3)δppm:6.58(s,2H),5.46(s,2H),3.176(s,2H), 1.57(s,)；
13C NMR(75MHz,CDCl3)δppm:169.9,137.0,82.2,48.7；
Photochemical reaction using light as new energy resource supply in a manner of, induced reaction substrate by ground state transition to higher energy level but
Still unionized excitation state generates high energy transient state reactive intermediate and significantly changes the reactivity of compound, has very high
Atom economy.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art within the technical scope of the present disclosure, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (6)
1. a kind of method of photocatalysis biology base furans Diels-Alder reaction, it is characterised in that: conjugated diene body biology base furan
Class of muttering compound 1 carries out Diels-Alder with dienophile compound 2 and reacts, and generates 7- oxabicyclo [2.2.1] -5- heptene
Molecular skeleton compound 3.
2. a kind of method of photocatalysis biology base furans Diels-Alder reaction according to claim 1, feature exist
In: at room temperature, it is seen that under light irradiation, Ru (bpy)3 2+Under conditions of catalyst, reaction equation is
3. a kind of method of photocatalysis biology base furans Diels-Alder reaction according to claim 2, feature exist
In: the electron-withdrawing substituent GDE of the compound 1 is electron-donating group H and/or CH3, and the electrophilic of the compound 2 takes
It is COR and/or CO for base EWG2R。
4. a kind of method of photocatalysis biology base furans Diels-Alder reaction according to claim 2, feature exist
In including the following steps:
(1) under the radiation of visible light for containing 365nm wavelength with specific wavelength, ruthenium complex Ru (bpy)3 2+It absorbs in light wave
One electronically form+divalent radical cation Ru (bpy)3 2+, the metal complex and dienophile maleic anhydride
After LUMO rail effect, excites an electronics in LUMO track to give metal complex, metal complex is reduced to+1 valence
Metal complex Ru (bpy)3 1+, while maleic anhydride conversion becomes dienophile radical cation；Then in O2Effect
Under, by the metal complex Ru (bpy) of+1 valence3 1+Oxidation obtains+divalent metal complex Ru (bpy)3 2+, make the metal combination
Object enters next illumination oxidation cycle；
(2) the LUMO track of maleic anhydride dienophile radical cation is combined with the HOMO track of diene body furans, hair
[4+2] pericyclic reaction is given birth to get 7- oxabicyclo [2.2.1] -5- heptene molecular skeleton compound 3 is arrived, meanwhile, free radical electronics
It is transmitted, obtains bridged ring radical cation midbody compound 3·+；
(3) by base cation midbody compound 3·+Free-radical oxidation reaction is carried out for dienophile raw material maleic anhydride, is obtained
To an electronics, target neutral molecule 7- oxabicyclo [2.2.1] -5- heptene molecular skeleton compound 3 is transformed into.
5. a kind of application of photocatalysis biology base furans Diels-Alder reaction, which is characterized in that specific reaction equation are as follows:
6. a kind of application of photocatalysis biology base furans Diels-Alder reaction according to claim 5, feature exist
In including the following steps:
(1) according to molal weight ratio by furans: maleic anhydride: (2,2'- bipyridyl) ruthenous chloride is that dress is added in 1:1.5:0.005
There is the round-bottomed flask of stirrer, be passed through oxygen after degassing, is placed in high-pressure sodium lamp in room temperature reaction；
(2) in above-mentioned reaction, reaction process is monitored by chromatographic sheet (TLC)；
(3) it is monitored by TLC and stops reacting after reaction raw materials furans completely disappears, reaction solution is extracted through ethyl acetate, saturation is eaten
The organic matter extraction phase obtained after salt water washing, concentration, it is dry with anhydrous sodium sulfate, using filter, concentration, recrystallization to get
7- oxygen two rings [2.2.1] hexane derivative compound 6.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892562A (en) * | 2020-08-13 | 2020-11-06 | 中国科学院山西煤炭化学研究所 | Method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride |
-
2019
- 2019-05-29 CN CN201910455668.8A patent/CN110128438A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| DIRK ALPERS ET AL.: "Photoassisted Oxidation of Ruthenium(II)-Photocatalysts Ru(bpy)32+ and Ru(bpz)32+ to RuO4: Orthogonal Tandem Photoredox and Oxidation Catalysis", 《CHEM. COMM.》 * |
| 胡仲禹等: "马来酸酐和呋喃的Diels-Alder 反应研究", 《江西化工》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892562A (en) * | 2020-08-13 | 2020-11-06 | 中国科学院山西煤炭化学研究所 | Method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride |
| CN111892562B (en) * | 2020-08-13 | 2022-09-09 | 中国科学院山西煤炭化学研究所 | Method for synthesizing phthalic anhydride by catalyzing furan and maleic anhydride |
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Application publication date: 20190816 |