CN108129308A - A kind of method that nontransition metal visible light catalytic halogenated aryl hydrocarbon and carbonyl source prepare ester - Google Patents
A kind of method that nontransition metal visible light catalytic halogenated aryl hydrocarbon and carbonyl source prepare ester Download PDFInfo
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- CN108129308A CN108129308A CN201810018704.XA CN201810018704A CN108129308A CN 108129308 A CN108129308 A CN 108129308A CN 201810018704 A CN201810018704 A CN 201810018704A CN 108129308 A CN108129308 A CN 108129308A
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- halogenated aryl
- aryl hydrocarbon
- visible light
- carbonyl source
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- C07—ORGANIC CHEMISTRY
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
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Abstract
The invention discloses a kind of methods that nontransition metal visible light catalytic halogenated aryl hydrocarbon and carbonyl source prepare ester., with potassium tert-butoxide derivative and 1, the complex that 10 phenanthroline derivatives are formed is photochemical catalyst for it, and carbon monoxide is carbonyl source, and halogenated aryl hydrocarbon and its derivative are reaction substrate, generate ester through free radical process under light illumination.The present invention replaces original noble metal catalyst using the organic coordination compound that no metal participates in, excited by visible light pattern replaces traditional mode of heating, green, the economic and efficient carbonylation for realizing halogenated aryl hydrocarbon, synthesis condition is mild, raw material is cheap and easy to get, it is environmentally friendly, efficiently using solar energy, have significant economic and social benefit.
Description
Technical field
The invention belongs to photocatalysis technical field of organic synthesis, and in particular to a kind of nontransition metal visible light catalytic is halogenated
The method that aromatic hydrocarbons and carbonyl source prepare ester.
Background technology
Sunlight is a kind of complex light, includes these three ultraviolet, visible and infrared different wave bands.Wherein 44% energy
Amount concentrates on visible light wave range.A long time ago, chemists found that chemical molecular absorb can obtain after light it is unique anti-
It should activity.Because visible ray has the advantages such as wavelength is suitable, natural abundance is big, if can be it will be seen that light be applied to organic synthesis
In, development potentiality is huge.Traditional organic synthesis is typically thermal response, until the middle and later periods in 19th century, it is seen that photocatalysis is just gradual
It applies in organic reaction, it is worth mentioning that, considerable photochemical reaction is directed to free radical mechanism.And carbonylation
It is then a kind of classical organic reaction, can synthesizes the carbonylation of various functional groups by introducing carbonyl group into reaction substrate
Close object, such as the compound of aldehyde, acid, ester and acid anhydrides containing carbonyl group.In recent years, due to the requirement of Green Chemistry, transition gold
Metal catalyst is a series of to report layer without transition metal-catalyzed organic reaction more and more by nontransition metal catalyst replaced
Go out not poor.
Light-catalyzed reaction is generally divided into ultraviolet light reaction and visible light reaction.Infrared ray is not enough to activate since wavelength is too long
Chemical bond can only cause the infrared vibration of molecule.Ultraviolet light photons energy is high, easily causes many side reactions, but absolutely mostly
Several simple organic molecules can only absorb the energy of ultraviolet band, it is impossible to by excited by visible light.Therefore visible light application to change
It learns in reaction, the mode that traditional heating etc. is replaced to energize, not only reaction condition is mild, side reaction is few, and reaction has
Higher stereoselectivity.On the other hand, sunlight is a kind of inexhaustible, nexhaustible energy, and reaches earth surface
The sunlight overwhelming majority be visible light wave range and not ultraviolet light.So visible ray, which is introduced into organic reaction, to be had greatly
Potential using value, but it is also a very challenging task.
The reaction of carbonyl is introduced into organic compound can broadly be known as carbonylation.Classical carbonylation
Usually it is made of electrophilic reagent, nucleopilic reagent and carbon monoxide source three.Electrophilic reagent can be halogenated aryl hydrocarbon and halogenated
Alkene or Pseudohalides, nucleopilic reagent then develop to hydrogen, silicon hydrogen, aromatic hydrocarbons and alkene etc. from the alcohol of early stage, amine, water etc..
Under carbon monoxide atmosphere, using halogenated aryl hydrocarbon as electrophilic reagent, different nucleopilic reagents is added in into reaction system can generate phase
A series of diversified carbonyls such as aryl acid, aryl ester, the aryl amide answered.
Invention content
The purpose of the present invention is using nontransition metal as catalyst, traditional mode of heating is replaced with excited by visible light,
Green, the synthesis for realizing ester efficiently, economic.Mild condition of the present invention, raw material is cheap and easy to get, low environment pollution has significantly
Economic benefit and social benefit.
For achieving the above object, the present invention is to be implemented by following technical solution：
A kind of method that nontransition metal visible light catalytic halogenated aryl hydrocarbon and carbonyl source prepare ester：Using benzene as solvent, by non-transition
After metallic catalyst, carbonyl source are mixed with halogenated aryl hydrocarbon, in minisize light-catalyzed autoclave, phase is generated through visible light catalytic
The ester answered.
The visible ray is ordinary light source of the wavelength in 400 ~ 800nm.
The nontransition metal catalyst be potassium tert-butoxide and the catalyst system of phenanthroline and its derivative,
In, the derivative of phenanthroline includes 5- nitro -1,10- phenanthrolines, 5- amino -1,10- phenanthrolines, 5- acrylamides
One kind in base -1,10- phenanthrolines.
The halogenated aryl hydrocarbon is included to one kind in iodotoluene, parachlorotoluene, ortho-chlorotolu'ene.
The carbonyl source includes one kind in carbon monoxide, hexacarbonylmolybdenum, six carbonyl irons, dimethylformamide.
More specifically：
A kind of method that nontransition metal visible light catalytic halogenated aryl hydrocarbon and carbonyl source prepare ester, the specific steps are：
（1）Reactant is loaded
Reaction is carried out in clean, dry minisize light-catalyzed autoclave.Reactor is first subjected to specially treated, then
Ready drug, reaction kettle etc. are moved into nitrogen glove box and carry out sample-adding operation.Nontransition metal catalyst is weighed first,
Then solvent benzol and halogenated aryl hydrocarbon are sequentially added with liquid-transfering gun；
（2）Reactant reaction
After the completion of sample-adding, the water removal of deoxygenation in 24 hours is placed in glove box, draught cupboard is then moved to from glove box, it is follow-up real
It tests and is carried out in draught cupboard.Nitrogen in reaction kettle is rinsed into line replacement with CO gas first, after flushing three times, to
It pours a certain amount of CO gases in reaction kettle, closes two-port valve, start to stir and with visible ray illumination reaction；
（3）Reaction product detects
Reaction after a certain period of time, stops illumination and stirring, and release the CO gases in reaction kettle, centrifuging and taking supernatant liquid.
Reaction solution carries out qualitative detection with GC-MS, finally carries out calculation of yield to target product with GC.
The advantage of the invention is that：
1）The present invention avoids as catalyst with potassium tert-butoxide and phenanthroline cheap and easy to get and its spreading out using conventional precious metal
Biology absorbs visible light-initiated subsequent reactions, and catalyst can recycle, and be easily recycled, and both save as photoresponse unit
About cost, and be conducive to the purification of late phase reaction object；
2）The present invention substitutes traditional heating condition using illumination condition, and efficiently using solar energy, reaction condition is mild, reduces ring
Border is polluted, and reduces reaction cost；
3）Reaction substrate applicability is extensive in the present invention, and yield is higher, and selectivity is good；Product is easy to purify.With preferable
Practical application potentiality；
4）The preparation method of the present invention is simple to operation, is conducive to promote and apply.
Specific embodiment
Embodiment is set forth below to further illustrate the present invention.
Embodiment 1
A kind of method that nontransition metal visible light catalytic halogenated aryl hydrocarbon and carbonyl source prepare ester, the specific steps are：
1）Potassium tert-butoxide 561mg (5mmol), 1,10- phenanthroline are added in clean, the dry, autoclave with magneton
90mg（0.5mmol）, anhydrous benzene 4ml, to iodotoluene 1mmol；
2）Reaction kettle is sealed after adding sample, is moved in draught cupboard from glove box, notices that subsequent operation is being divulged information
It is carried out in cupboard, first with the CO gas bleeds reaction kettle of certain pressure so as to, into line replacement, rinse three to the nitrogen in reaction kettle
After secondary, 60atmCO gases are filled with into reaction kettle, close two-port valve；
3）Start to stir and carry out visible light reaction with xenon lamp（420nm ＜ λ ＜ 780nm, 500mWcm2）, after reaction for 24 hours, stop
Illumination and stirring, and discharge the CO gases in reaction kettle.
Embodiment 2
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the carbon monoxide pressure of 60atm
10atm。
Embodiment 3
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the carbon monoxide pressure of 60atm
20atm。
Embodiment 4
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the carbon monoxide pressure of 60atm
30atm。
Embodiment 5
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the carbon monoxide pressure of 60atm
40atm。
Embodiment 6
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the carbon monoxide pressure of 60atm
50atm。
Embodiment 7
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the carbon monoxide pressure of 60atm
70atm。
Embodiment 8
Specific experiment method and this part example 1 are essentially identical, and the difference lies in the reaction time is changed to 8h for 24 hours.
Embodiment 9
Specific experiment method and this part example 1 are essentially identical, and the difference lies in the reaction time is changed to 16h for 24 hours.
Embodiment 10
Specific experiment method and this part example 1 are essentially identical, and the difference lies in the reaction time is changed to 32h for 24 hours.
Embodiment 11
Specific experiment method and this part embodiment 1 are essentially identical, and the difference lies in the reaction time is changed to 40h for 24 hours.
Embodiment 12
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the amount of potassium tert-butoxide by 5mmol
3mmol。
Embodiment 13
Specific experiment method and this part example 1 are essentially identical, and the difference lies in be changed to the amount of potassium tert-butoxide by 5mmol
4mmol。
Embodiment 14
Specific experiment method and this part example 1 are essentially identical, and the difference lies in potassium tert-butoxide is changed to sodium tert-butoxide.
Embodiment 15
Specific experiment method and this part example 1 are essentially identical, the difference lies in by the amount of 1,10 Phen by 0.5mmol
It is changed to 0mmol.
Embodiment 16
Specific experiment method and this part example 1 are essentially identical, the difference lies in by the amount of 1,10 Phen by 0.5mmol
It is changed to 0.2mmol.
Embodiment 17
Specific experiment method and this part example 1 are essentially identical, the difference lies in by the amount of 1,10 Phen by 0.5mmol
It is changed to 0.4mmol.
Embodiment 18
Specific experiment method and this part example 1 are essentially identical, the difference lies in by the amount of 1,10 Phen by 0.5mmol
It is changed to 0.6mmol.
Embodiment 19
Specific experiment method and this part example 1 are essentially identical, and the difference lies in will be seen that light illumination reaction to for dark reaction.
Embodiment 20
Specific experiment method and this part example 1 are essentially identical, and the difference lies in will be seen that light illumination reaction is changed to ultraviolet light
Illumination reaction.
Embodiment 21
Specific experiment method and this part example 1 are essentially identical, and the difference lies in CO is changed to Mo (CO)6。
Embodiment 22
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 1,10- Phens are changed to 4,7- hexichol
Base -1,10- Phens.
Embodiment 23
Specific experiment method and this part example 1 are essentially identical, and the difference lies in by ButOK/1,10- Phen/benzene body
System is changed to ButOK/DMSO systems.
Embodiment 24
Specific experiment method and this part example 1 are essentially identical, and the difference lies in benzene is changed to DMSO.
Embodiment 25
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 2- iodo toluene will be changed to iodotoluene.
Embodiment 26
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 3- iodo toluene will be changed to iodotoluene.
Embodiment 27
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 4- bromotoluenes will be changed to iodotoluene.
Embodiment 28
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 2- bromotoluenes will be changed to iodotoluene.
Embodiment 29
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 3- bromotoluenes will be changed to iodotoluene.
Embodiment 30
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 4- chlorotoluenes will be changed to iodotoluene.
Embodiment 31
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 2- chlorotoluenes will be changed to iodotoluene.
Embodiment 32
Specific experiment method and this part example 1 are essentially identical, and the difference lies in 3- chlorotoluenes will be changed to iodotoluene.
Embodiment 33
Specific experiment method and this part example 1 are essentially identical, and the difference lies in will be changed to benzyl chloride to iodotoluene.
Table 1：The halogenated aryl hydrocarbon carbonylation carried out using different experiments method
The foregoing is merely presently preferred embodiments of the present invention, and all equivalent changes done according to scope of the present invention patent are with repairing
Decorations should all belong to the covering scope of the present invention.
Claims (5)
1. a kind of method that nontransition metal visible light catalytic halogenated aryl hydrocarbon and carbonyl source prepare ester, it is characterised in that：Using benzene as
Solvent, after nontransition metal catalyst, carbonyl source are mixed with halogenated aryl hydrocarbon, in minisize light-catalyzed autoclave, through can
See that photocatalysis generates corresponding ester.
2. a kind of nontransition metal visible light catalytic halogenated aryl hydrocarbon according to claim 1 and carbonyl source prepare the side of ester
Method, it is characterised in that：The visible ray is ordinary light source of the wavelength in 400 ~ 800nm.
3. according to the method that a kind of nontransition metal visible light catalytic halogenated aryl hydrocarbon described in claim 1 and carbonyl source prepare ester,
It is characterized in that：The nontransition metal catalyst be potassium tert-butoxide and the catalyst system of phenanthroline and its derivative,
Wherein, the derivative of phenanthroline includes 5- nitro -1,10- phenanthrolines, 5- amino -1,10- phenanthrolines, 5- acrylamides
One kind in base -1,10- phenanthrolines.
4. according to the method that a kind of nontransition metal visible light catalytic halogenated aryl hydrocarbon described in claim 1 and carbonyl source prepare ester,
It is characterized in that：The halogenated aryl hydrocarbon is included to one kind in iodotoluene, parachlorotoluene, ortho-chlorotolu'ene.
5. according to the method that a kind of nontransition metal visible light catalytic halogenated aryl hydrocarbon described in claim 1 and carbonyl source prepare ester,
It is characterized in that：The carbonyl source includes one kind in carbon monoxide, hexacarbonylmolybdenum, six carbonyl irons, dimethylformamide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776422A (en) * | 2019-11-13 | 2020-02-11 | 福州大学 | Method for preparing ester by irradiating halogenated aromatic hydrocarbon, alcohol and carbonyl source by ultraviolet light |
| CN112403525A (en) * | 2020-12-03 | 2021-02-26 | 大连理工大学 | Preparation method and application of metal organic framework catalyst with ligand molecule internal and external structures |
Citations (2)
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| CN1562950A (en) * | 2004-04-08 | 2005-01-12 | 大连大学 | Method of alkane halide carbonylation reaction under photic acceleration and catalysis of non noble metal |
| CN101456815A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing aromatic carboxylic ether by iodo aromatic hydrocarbon acarbonylation |
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2018
- 2018-01-09 CN CN201810018704.XA patent/CN108129308A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1562950A (en) * | 2004-04-08 | 2005-01-12 | 大连大学 | Method of alkane halide carbonylation reaction under photic acceleration and catalysis of non noble metal |
| CN101456815A (en) * | 2007-12-13 | 2009-06-17 | 中国科学院兰州化学物理研究所 | Method for synthesizing aromatic carboxylic ether by iodo aromatic hydrocarbon acarbonylation |
Non-Patent Citations (1)
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| ZHANG HUA等: ""Transition-Metal-Free Alkoxycarbonylation of Aryl Halides"", 《ANGEWANDTE CHEMIE INTERNATIONAL EDITION》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110776422A (en) * | 2019-11-13 | 2020-02-11 | 福州大学 | Method for preparing ester by irradiating halogenated aromatic hydrocarbon, alcohol and carbonyl source by ultraviolet light |
| CN110776422B (en) * | 2019-11-13 | 2021-07-27 | 福州大学 | Method for preparing ester by irradiating halogenated aromatic hydrocarbon, alcohol and carbonyl source by ultraviolet light |
| CN112403525A (en) * | 2020-12-03 | 2021-02-26 | 大连理工大学 | Preparation method and application of metal organic framework catalyst with ligand molecule internal and external structures |
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