CN109942364A - It is a kind of using water as the olefin synthesis process of hydrogen source - Google Patents
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Abstract
The invention discloses a kind of using water as the olefin synthesis process of hydrogen source.Alkynes is synthesis material within this method, and cobalt compound is catalyst, and water is hydrogen source, synthesizes alkene by transfer hydrogenation.In the present invention, cis-form olefin can be obtained if any ligand is not added with trans olefins by biphosphine ligand being added in the reaction system.The present invention provides a kind of high-efficiency synthesis methods of the cis/trans formula alkene of mild, efficient, pervasive and controllable chemo-selective.
Description
Technical field
The invention belongs to technical field of organic synthesis, and in particular to a kind of using water as the olefin synthesis process of hydrogen source.
Background technique
Highly selective alkynes semi-reduction hydrogenation reaction is to obtain the important method of single configuration alkene, in recent decades,
Precious metal catalyst hydrogenation (such as classical Lin Dela palladium catalyst) is depended on, therefore, exploitation and development cheap metal catalysis
Agent and more green, economic hydrogen source have a very important significance.It is more to obtain in the semi-reduction hydrogenation reaction of alkynes
The olefin product of single configuration, it is desirable that there is high reaction selectivity.Therefore, regulatable highly selective semi-reduction hydrogenation catalyst
The project for being configured to vast researcher and being worth challenge of system.Water is one of most common substance in nature, because of it
Cheap and environmental protection key property, is optimal hydrogen source, is had using water as the transfer hydrogenation of hydrogen source economic and environment-friendly, warm
With efficient feature.
In natural products and drug molecular structure, the cis-trans isomerization of alkene is widely present, and is such as distributed widely in each
Diphenylethylene natural products in class plant is mainly anti-configuration, is existed mostly in the form of aglycon or glycosides, and is commonly formed anti-
The 3 of formula, 4 ', the skeleton and its derivative of 5- trihydroxy talan (resveratrol).Trans- diphenylethylene compounds are past
Toward a variety of important bioactivity such as anti-senile dementia, anticancer, antibacterial, anti-oxidant, the reduction blood lipids having, cause both at home and abroad
The great attention and further investigation of scholar.In pharmaceutical chemistry, cis-form olefin represents a kind of important pharmacophore, extensively
It is present in many bioactive molecules, the 11- cis retinal (11- of key effect is such as played in the formation of human vision
Cis-retinal)；Antipsychotic drug Chlorprothixene (chlorprothixene), molecular structure contains double bond, thus in the presence of
Cis-trans-isomer, wherein cis- antipsycholic action is trans- eight times；It is isolated from the short raw willow bark in South Africa
CombretastatinA-4 shows stronger anti-tumor activity as effective Antitubulin, and the compound is only
It is cis-configuration Shi Caiyou therapeutic effect.
As it can be seen that the method that high selectivity specifies configuration alkene structures has broad application prospect, using cheap gold
Belong to catalysis, building is economical, environmentally friendly, highly selective catalyst system has a very important significance.
Summary of the invention
The purpose of the present invention is to provide a kind of using water as the olefin synthesis process of hydrogen source.
The object of the present invention is achieved like this, it is described be as the olefin synthesis process of hydrogen source using water within alkynes be synthesis
Raw material, cobalt compound are catalyst, and water is hydrogen source, synthesize alkene by transfer hydrogenation.
The present invention be a kind of catalysis of cheap metal, using water as hydrogen source, easy to operate, reaction is mild efficiently, universality is good
The high-selectivity synthesis method of cis/trans alkene.
The present invention is realized using following technical scheme:
1, the Co catalysts used have cobaltous iodide, cobaltous bromide, cobalt chloride, cobalt acetate, acetylacetone cobalt etc..
2, the ligand used has biphosphine ligand: dppe, dppm, dppp, dppb, dppf, dppen, XantPhos, rac-
Binap, dinitrogen ligand: 1,10-phen, monophosphorus ligand: PPh3, molecular structure is respectively:
。
3, the molecular structure of interior alkynes is:
。
4, alkynes is the high-selectivity synthesis method packet for the cis/trans formula alkene that starting material cobalt is catalyzed using water as hydrogen source within
Include following steps:
The synthesis step of cis-form olefin:
(1) alkynes is raw material within, in glove box, by precise cobaltous iodide (0.01 mmol), reducing agent zinc powder (0.6
Mmol), any one interior alkynes (0.2 mmol), sequentially adds into the history Neck reaction tube for having stirrer, and rubber plug removes beyond the Great Wall
Glove box.
(2) 2mL methanol and 36 μ L water are drawn, are sequentially added into reaction tube.It is placed at 60 DEG C of constant temperature blender with magnetic force and stirs
Reaction is mixed, reaction process is monitored using TLC.
(3) after reaction, reaction tube is taken out, reaction solution removes volatile solvent under reduced pressure, passes through column chromatographic purifying
Obtain cis-form olefin.
The synthesis step of trans olefins:
(1) alkynes is raw material within, in glove box, by precise cobaltous iodide (0.01mmol), dppe ligand (0.012
Mmol it) is added into the history Neck reaction tube for having stirrer, after addition 1mL acetonitrile is dissolved, is placed in magnetic stirring apparatus room temperature
Lower stirring 30min.
(2) precise reducing agent zinc (0.6 mmol), alkynes (0.2 mmol) in any one aryl are added sequentially to anti-
Ying Guanzhong, and 1mL acetonitrile is added, rubber plug removes glove box beyond the Great Wall.
(3) 36 μ L(2 mmol are drawn) water is added to reaction tube.It is placed at 60 DEG C of constant temperature blender with magnetic force and is stirred to react, adopt
Reaction process is monitored with TLC.
(4) after reaction, reaction tube is taken out, reaction solution removes volatile solvent under reduced pressure, passes through column chromatographic purifying
Obtain trans olefins.
The above process can be indicated using following chemical equations:
。
In above-mentioned steps, metallic catalyst be cobaltous iodide, cobaltous bromide, cobalt chloride, cobalt acetate, acetylacetone cobalt it is any one
Kind, wherein it is preferred that metallic catalyst is cobaltous iodide.
In the synthesis step of above-mentioned cis-form olefin, solvent for use is methanol, ethyl alcohol, isopropanol, trifluoroethanol, acetonitrile, four
Hydrogen furans, dioxane, any one or a few in toluene, wherein preferred solvent is methanol.
In the synthesis step of above-mentioned trans olefins, solvent for use is acetonitrile, tetrahydrofuran, dioxane, toluene, N, N- bis-
Methylformamide, two sulphur sulfoxides, any one or a few in methanol, wherein preferred solvent is acetonitrile.
In the synthesis step of above-mentioned trans olefins, ligand used be biphosphine ligand: dppe, dppm, dppp, dppb, dppf,
Dppen, XantPhos, rac-Binap, dinitrogen ligand: 1,10-phen, monophosphorus ligand: PPh3In any one, wherein excellent
Apolegamy body is dppe.
In above-mentioned steps, reducing agent used has one or more of the zinc powder of metal simple-substance, manganese powder, magnesium powder, iron powder,
Wherein preferred reducing agent is zinc powder.
It can be had the advantages that compared with prior art with the technical solution adopted by the present invention
1. the present invention using using cheap transition metals cobalt catalysis strategy, using water as hydrogen source, it is highly selective prepare it is cis- or
Trans- olefin(e) compound can substantially reduce production cost, have significant Social benefit and economic benefit.
2. catalyst system of the present invention is simple, easy to operate, selective good.
3. the present invention, by adjusting ligand and solvent condition, can realize reaction product configuration under the catalysis of cobaltous iodide
High selection regulation.
Specific embodiment
Below with reference to embodiment, the present invention is further illustrated, but the present invention is limited in any way,
Based on present invention teach that it is made it is any transform or replace, all belong to the scope of protection of the present invention.
It is of the present invention be as the olefin synthesis process of hydrogen source using water within alkynes be synthesis material, cobalt compound is catalysis
Agent, water are hydrogen source, synthesize alkene by transfer hydrogenation.
Described includes cis-form olefin synthetic method and trans olefins synthetic method by the olefin synthesis process of hydrogen source of water.
The cis-form olefin synthetic method the following steps are included:
A, by cobalt compound, reducing agent and interior alkynes in molar ratio it is first 1:(50 ~ 70): the ratio of (10 ~ 30) is sequentially added to anti-
It answers and obtains material a in container；
B, it is (100 ~ 300): 1 methanol and mole body that cobalt compound molal volume ratio (ml:mmol) is sequentially added in material a
Product is (3000 ~ 4000) than (μ l:mmol): 1 water, then constant temperature is stirred to react at 50 ~ 70 DEG C of temperature, is monitored using TLC
Reaction process, after reaction, reaction solution remove volatile solvent under reduced pressure, and it is cis- to obtain object by column chromatographic purifying
Alkene.
The trans olefins synthetic method the following steps are included:
A, first by cobalt compound and ligand 1:(1 ~ 1.5 in molar ratio) ratio sequentially add to reaction vessel, add cobalt
Closing object molal volume ratio (ml:mmol) is (50 ~ 150): 1 acetonitrile stirs 20 ~ 40min and obtains material a to after dissolving；
B, sequentially adding in material a with cobalt compound molar ratio is 1:(50 ~ 70): the reducing agent and interior alkynes of (10 ~ 30), then mend
Adding cobalt compound molal volume ratio (ml:mmol) is (50 ~ 150): 1 acetonitrile obtains material b；
C, it is (3000 ~ 4000): 1 water that molal volume ratio (μ l:mmol) is added in material b, then at 50 ~ 70 DEG C of temperature
Constant temperature is stirred to react, and monitors reaction process using TLC, after reaction, reaction solution removes volatile solvent under reduced pressure, passes through
Column chromatographic purifying obtains object trans olefins.
The cobalt compound is one or more of cobaltous iodide, cobaltous bromide, cobalt chloride, acetylacetone cobalt, cobalt acetate.
The reducing agent is one or more of metal simple-substance zinc powder, manganese powder, magnesium powder or iron powder.
The interior alkynes is alkynes in diaryl, alkynes in single araliphatic, alkynes in alkynes ester or fat in single aryl.
The ligand is dppe, dppm, dppp, dppb, dppf, dppen, XantPhos, rac-Binap, 1,10-
Phen or PPh3。
Case is embodied, the present invention will be further described below:
Embodiment 1
It is successively that cobaltous iodide (0.01 mmol), zinc powder (0.6 mmol), above-mentioned alkynes (0.2 mmol) is accurate in glove box
In the history Neck reaction tube for weighing and being encased in stirrer, rubber plug removes glove box beyond the Great Wall, and syringe takes 2 ml methanol,
Microsyringe draws 36 μ L(2 mmol) water is added to reaction tube, is placed at 60 DEG C of constant temperature blender with magnetic force and is stirred to react, adopt
Reaction process is monitored with TLC.After reaction, it opens reactor and removes volatility object using rotary evaporator under reduced pressure
Matter uses ethyl acetate and petroleum ether as eluant, eluent, passes through column chromatographic purifying.Reaction dissolvent is concentrated under reduced pressure, carries out column later
Chromatographic purifying obtains diphenylethylene compounds (99% yield, Z/E=90:10).1H NMR (400 MHz, CDCl3)
δ 7.30 – 7.12 (m, 10H), 6.59 (s, 2H)。
Embodiment 2
It is successively that cobaltous iodide (0.01 mmol), zinc powder (0.6 mmol), above-mentioned alkynes (0.2 mmol) is accurate in glove box
In the history Neck reaction tube for weighing and being encased in stirrer, rubber plug removes glove box beyond the Great Wall, and syringe takes 2 ml methanol,
Microsyringe draws 36 μ L(2 mmol) water is added to reaction tube, is placed at 60 DEG C of constant temperature blender with magnetic force and is stirred to react, adopt
Reaction process is monitored with TLC.After reaction, it opens reactor and removes volatility object using rotary evaporator under reduced pressure
Matter uses ethyl acetate and petroleum ether as eluant, eluent, passes through column chromatographic purifying.Reaction dissolvent is concentrated under reduced pressure, carries out column later
Chromatographic purifying obtains diphenylethylene compounds (96% yield, Z/E:90:10).1H NMR (400 MHz, CDCl3) δ
7.28 – 7.14 (m, 7H), 6.74 (d, J = 8.8 Hz, 2H), 6.51 (s, 2H), 3.76 (s, 3H)。
Embodiment 3
It is successively that cobaltous iodide (0.01 mmol), zinc powder (0.6 mmol), above-mentioned alkynes (0.2 mmol) is accurate in glove box
In the history Neck reaction tube for weighing and being encased in stirrer, rubber plug removes glove box beyond the Great Wall, and syringe takes 2 ml methanol,
Microsyringe draws 36 μ L(2 mmol) water is added to reaction tube, is placed at 60 DEG C of constant temperature blender with magnetic force and is stirred to react, adopt
Reaction process is monitored with TLC.After reaction, it opens reactor and removes volatility object using rotary evaporator under reduced pressure
Matter uses ethyl acetate and petroleum ether as eluant, eluent, passes through column chromatographic purifying.Reaction dissolvent is concentrated under reduced pressure, carries out column later
Chromatographic purifying obtains diphenylethylene compounds (98% yield, Z/E=91:9).1H NMR (400 MHz, CDCl3) δ
7.33 (d, J = 8.4 Hz, 2H), 7.26 – 7.18 (m, 5H), 7.10 (d, J = 8.3 Hz, 2H), 6.56
(dd, J = 52.0, 12.2 Hz, 2H)。
Embodiment 4
In glove box, by cobaltous iodide (0.01 mmol), dppe(0.012 mmol) precise and it is encased in stirrer
In history Neck reaction tube, after addition 1mL acetonitrile is dissolved, it is placed under magnetic stirring apparatus room temperature and stirs 30min, fill complexing
Point.Precise zinc powder (0.6 mmol), above-mentioned interior alkynes (0.2 mmol) are added sequentially in reaction tube, and add 1mL second afterwards
Nitrile, rubber plug removes glove box beyond the Great Wall.Microsyringe draws 36 μ L(2 mmol) water is added to reaction tube, is placed in constant temperature magnetic force and stirs
It mixes and is stirred to react at 60 DEG C of device, reaction process is monitored using TLC.After reaction, reactor is opened and under reduced pressure using rotation
Turn evaporator and remove volatile materials, uses ethyl acetate and petroleum ether as eluant, eluent, pass through column chromatographic purifying.By reaction dissolvent
It is concentrated under reduced pressure, carries out column chromatographic purifying later, obtain diphenylethylene compounds (99% yield, Z/E=97:3).1H
NMR (400 MHz, CDCl3) δ 7.50 (d, J = 7.7 Hz, 4H), 7.34 (t, J = 7.6 Hz, 4H),
7.25 (dd, J = 8.4, 6.2 Hz, 2H), 7.10 (d, J = 2.4 Hz, 2H)。
Embodiment 5
In glove box, by cobaltous iodide (0.01 mmol), dppe(0.012 mmol) precise and it is encased in stirrer
In history Neck reaction tube, after addition 1mL acetonitrile is dissolved, it is placed under magnetic stirring apparatus room temperature and stirs 30min, fill complexing
Point.Precise zinc powder (0.6 mmol), above-mentioned interior alkynes (0.2 mmol) are added sequentially in reaction tube, and add 1mL second afterwards
Nitrile, rubber plug removes glove box beyond the Great Wall.Microsyringe draws 36 μ L(2 mmol) water is added to reaction tube, is placed in constant temperature magnetic force and stirs
It mixes and is stirred to react at 60 DEG C of device, reaction process is monitored using TLC.After reaction, reactor is opened and under reduced pressure using rotation
Turn evaporator and remove volatile materials, uses ethyl acetate and petroleum ether as eluant, eluent, pass through column chromatographic purifying.By reaction dissolvent
It is concentrated under reduced pressure, carries out column chromatographic purifying later, obtain diphenylethylene compounds (98% yield, Z/E=7:93).1H
NMR (400 MHz, CDCl3) δ 7.46 (dd, J = 14.5, 8.0 Hz, 4H), 7.33 (t, J = 7.6 Hz,
2H), 7.25 – 7.19 (m, 1H), 7.01 (dd, J = 38.4, 16.3 Hz, 2H), 6.89 (d, J = 8.8
Hz, 2H), 3.80 (s, 3H)。
Embodiment 6
In glove box, by cobaltous iodide (0.01 mmol), dppe(0.012 mmol) precise and it is encased in stirrer
In history Neck reaction tube, after addition 1mL acetonitrile is dissolved, it is placed under magnetic stirring apparatus room temperature and stirs 30min, fill complexing
Point.Precise zinc powder (0.6 mmol), above-mentioned interior alkynes (0.2 mmol) are added sequentially in reaction tube, and add 1mL second afterwards
Nitrile, rubber plug removes glove box beyond the Great Wall.Microsyringe draws 36 μ L(2 mmol) water is added to reaction tube, is placed in constant temperature magnetic force and stirs
It mixes and is stirred to react at 60 DEG C of device, reaction process is monitored using TLC.After reaction, reactor is opened and under reduced pressure using rotation
Turn evaporator and remove volatile materials, uses ethyl acetate and petroleum ether as eluant, eluent, pass through column chromatographic purifying.By reaction dissolvent
It is concentrated under reduced pressure, carries out column chromatographic purifying later, obtain diphenylethylene compounds (70% yield, Z/E=5:95).1H
NMR (400 MHz, CDCl3) δ 7.56 – 7.45 (m, 4H), 7.38 (dd, J = 8.1, 6.2 Hz, 4H),
7.32 – 7.26 (m, 1H), 7.07 (q, J = 16.3 Hz, 2H)。
The above embodiments merely illustrate the technical concept and features of the present invention, and all Spirit Essences according to the present invention are made
Equivalent change or modification out, is all included within the scope of the present invention.
Claims (8)
1. a kind of using water as the olefin synthesis process of hydrogen source, it is characterised in that described to be by the olefin synthesis process of hydrogen source of water
Within alkynes be synthesis material, cobalt compound is catalyst, and water is hydrogen source, synthesizes alkene by transfer hydrogenation.
2. according to claim 1 using water as the olefin synthesis process of hydrogen source, it is characterised in that described using water as hydrogen source
Olefin synthesis process include cis-form olefin synthetic method and trans olefins synthetic method.
3. according to claim 2 using water as the olefin synthesis process of hydrogen source, it is characterised in that the cis-form olefin closes
At method the following steps are included:
A, by cobalt compound, reducing agent and interior alkynes in molar ratio it is first 1:(50 ~ 70): the ratio of (10 ~ 30) is sequentially added to anti-
It answers and obtains material a in container；
B, it is (100 ~ 300): 1 methanol and mole body that cobalt compound molal volume ratio (ml:mmol) is sequentially added in material a
Product is (3000 ~ 4000) than (μ l:mmol): 1 water, then constant temperature is stirred to react at 50 ~ 70 DEG C of temperature, is monitored using TLC
Reaction process, after reaction, reaction solution remove volatile solvent under reduced pressure, and it is cis- to obtain object by column chromatographic purifying
Alkene.
4. according to claim 2 using water as the olefin synthesis process of hydrogen source, it is characterised in that the trans olefins close
At method the following steps are included:
A, first by cobalt compound and ligand 1:(1 ~ 1.5 in molar ratio) ratio sequentially add to reaction vessel, add cobalt
Closing object molal volume ratio (ml:mmol) is (50 ~ 150): 1 acetonitrile stirs 20 ~ 40min and obtains material a to after dissolving；
B, sequentially adding in material a with cobalt compound molar ratio is 1:(50 ~ 70): the reducing agent and interior alkynes of (10 ~ 30), then mend
Adding cobalt compound molal volume ratio (ml:mmol) is (50 ~ 150): 1 acetonitrile obtains material b；
C, it is (3000 ~ 4000): 1 water that molal volume ratio (μ l:mmol) is added in material b, then at 50 ~ 70 DEG C of temperature
Constant temperature is stirred to react, and monitors reaction process using TLC, after reaction, reaction solution removes volatile solvent under reduced pressure, passes through
Column chromatographic purifying obtains object trans olefins.
5. according to claim 3 or 4 using water as the olefin synthesis process of hydrogen source, it is characterised in that the cobalt compound
For one or more of cobaltous iodide, cobaltous bromide, cobalt chloride, acetylacetone cobalt, cobalt acetate.
6. according to claim 3 or 4 using water as the olefin synthesis process of hydrogen source, it is characterised in that the reducing agent is
One or more of metal simple-substance zinc powder, manganese powder, magnesium powder or iron powder.
7. according to claim 3 or 4 using water as the olefin synthesis process of hydrogen source, it is characterised in that the interior alkynes is two
Alkynes in aryl, alkynes in single araliphatic, alkynes in alkynes ester or fat in single aryl.
8. according to claim 4 using water as the olefin synthesis process of hydrogen source, it is characterised in that the ligand be dppe,
Dppm, dppp, dppb, dppf, dppen, XantPhos, rac-Binap, 1,10-phen or PPh3。
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111606774A (en) * | 2020-07-01 | 2020-09-01 | 云南民族大学 | Method for efficiently preparing styrene and deuterated styrene compounds |
| CN113024340A (en) * | 2021-03-18 | 2021-06-25 | 长春工业大学 | Method for reducing alkyne into olefin by using water as hydrogen source under catalysis of nickel |
| CN113443952A (en) * | 2021-07-15 | 2021-09-28 | 南通大学 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water |
| CN113563150A (en) * | 2021-07-15 | 2021-10-29 | 南通大学 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through palladium on hydrogen supplied by water |
| CN114713283A (en) * | 2022-04-26 | 2022-07-08 | 沈阳药科大学 | Cobalt nanoparticle efficient selective catalytic system and method for reducing alkyne to generate (Z) -olefin by using same |
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2019
- 2019-04-12 CN CN201910291395.8A patent/CN109942364B/en active Active
Non-Patent Citations (10)
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111606774A (en) * | 2020-07-01 | 2020-09-01 | 云南民族大学 | Method for efficiently preparing styrene and deuterated styrene compounds |
| CN113024340A (en) * | 2021-03-18 | 2021-06-25 | 长春工业大学 | Method for reducing alkyne into olefin by using water as hydrogen source under catalysis of nickel |
| CN113024340B (en) * | 2021-03-18 | 2023-10-20 | 长春工业大学 | Method for reducing alkyne into olefin by using nickel catalytic water as hydrogen source |
| CN113443952A (en) * | 2021-07-15 | 2021-09-28 | 南通大学 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through iridium with hydrogen supplied by water |
| CN113563150A (en) * | 2021-07-15 | 2021-10-29 | 南通大学 | Method for selectively synthesizing cis-olefin and trans-olefin by catalyzing alkyne semi-reduction through palladium on hydrogen supplied by water |
| CN114713283A (en) * | 2022-04-26 | 2022-07-08 | 沈阳药科大学 | Cobalt nanoparticle efficient selective catalytic system and method for reducing alkyne to generate (Z) -olefin by using same |
| CN114713283B (en) * | 2022-04-26 | 2024-05-14 | 沈阳药科大学 | Cobalt nanoparticle high-efficiency selective catalytic system and method for generating (Z) -alkene by reducing alkyne by using same |
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