CN109942364B - Olefin synthesis method using water as hydrogen source - Google Patents
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Abstract
The invention discloses an olefin synthesis method taking water as a hydrogen source. The method takes alkyne as a synthetic raw material, a cobalt compound as a catalyst and water as a hydrogen source, and synthesizes olefin through transfer hydrogenation. In the invention, the diphosphine ligand is added into the reaction system to obtain trans-olefin, and if no ligand is added, cis-olefin is obtained. The invention provides a mild, high-efficiency, universal and controllable chemical selectivity efficient synthesis method of cis/trans olefins.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to an olefin synthesis method taking water as a hydrogen source.
Background
The semi-reduction hydrogenation reaction of high-selectivity alkyne is an important method for obtaining olefin with single configuration, and in recent decades, the semi-reduction hydrogenation reaction mainly depends on noble metal catalytic hydrogenation (such as a classical lindlar palladium catalyst), so that the development and development of cheap metal catalysts and more green and economic hydrogen sources have very important significance. In the semi-reduction hydrogenation reaction of alkyne, high reaction selectivity is required for obtaining more olefin products with single configuration. Therefore, the construction of the controllable high-selectivity semi-reduction hydrogenation catalytic system is a challenge for the majority of researchers. Water is one of the most common substances in nature, is the most ideal hydrogen source due to the important characteristics of low price and environmental protection, and the transfer hydrogenation reaction taking water as the hydrogen source has the characteristics of economy, environmental protection, mildness and high efficiency.
In the molecular structures of natural products and drugs, the cis-trans isomerization phenomenon of olefins widely exists, for example, stilbene natural products widely distributed in various plants mainly have trans-configuration, exist in the form of aglycon or glycoside, and often form the skeleton of trans-3, 4', 5-trihydroxy stilbene (resveratrol) and derivatives thereof. The trans-stilbene compounds often have a plurality of important biological activities of senile dementia resistance, cancer resistance, bacteria resistance, oxidation resistance, blood fat reduction and the like, and cause high attention and deep research of domestic and foreign scholars. In pharmaceutical chemistry, cis-olefins represent an important class of pharmacodynamic structures, widely present in a variety of biologically active molecules, such as 11-cis-retinal (11-cis-retinal), which plays a key role in the development of human vision; the antipsychotic chlorprothixene (chlorprothixene) which contains a double bond in its molecular structure such that cis-trans isomers exist in which cis-form is an octafold of trans-form in antipsychotic action; combretastatin A-4 isolated from the bark of Arthropoda nana shows strong anti-tumor activity as a potent tubulin inhibitor, and the compound has therapeutic effects only when it is in cis-configuration.
Therefore, the method for synthesizing the olefin structure with the specified configuration at high selectivity has wide application prospect, and has very important significance for constructing an economic, environment-friendly and high-selectivity catalytic system by adopting cheap metal catalysis.
Disclosure of Invention
The invention aims to provide an olefin synthesis method taking water as a hydrogen source.
The invention aims to realize the synthesis method of the olefin by taking water as a hydrogen source, which synthesizes the olefin by taking alkyne as a synthesis raw material, cobalt compound as a catalyst and water as the hydrogen source through transfer hydrogenation.
The invention is a high-selectivity synthesis method of cis/trans olefin, which has the advantages of low-cost metal catalysis, water as a hydrogen source, simple and convenient operation, mild and efficient reaction and good universality.
The invention is realized by adopting the following technical scheme:
1. the cobalt catalyst used is cobalt iodide, cobalt bromide, cobalt chloride, cobalt acetate, cobalt acetylacetonate, etc.
2. The ligands used are bisphosphine ligands: dppe, dppm, dppp, dppb, dppf, dppn, XantPhos, rac-Binap, bis-nitrogen ligand: 1, 10-phen, monophosphine ligand: PPh3The molecular structures are respectively as follows:
3. the molecular structure of the internal alkyne is:
4. the high-selectivity synthesis method of cis/trans olefin by taking internal alkyne as a starting material and water as a hydrogen source under the catalysis of cobalt comprises the following steps:
synthesis of cis-olefins:
(1) cobalt iodide (0.01 mmol), a reducing agent zinc powder (0.6 mmol) and any one of the alkynes (0.2 mmol) are accurately weighed in a glove box, and are sequentially added into a Schleneker reaction tube with a stirrer, and a rubber plug is plugged to remove the glove box.
(2) 2mL of methanol and 36. mu.L of water were aspirated and added to the reaction tube in this order. The reaction was stirred at 60 ℃ in a constant temperature magnetic stirrer and the progress of the reaction was monitored by TLC.
(3) After the reaction, the reaction tube was taken out, the volatile solvent was removed from the reaction solution under reduced pressure, and the cis-olefin was purified by column chromatography.
Synthesis of trans-olefin:
(1) taking internal alkyne as a raw material, adding accurately weighed cobalt iodide (0.01 mmol) and dppe ligand (0.012 mmol) into a Schlenk reaction tube with a stirrer in a glove box, adding 1mL of acetonitrile for dissolving, and then placing the mixture in a magnetic stirrer for stirring for 30min at normal temperature.
(2) Accurately weighing a reducing agent zinc (0.6 mmol) and any one of aryl alkynes (0.2 mmol), sequentially adding into a reaction tube, adding 1mL of acetonitrile, plugging a rubber plug, and removing from the glove box.
(3) mu.L (2 mmol) of water was pipetted into the reaction tube. The reaction was stirred at 60 ℃ in a constant temperature magnetic stirrer and the progress of the reaction was monitored by TLC.
(4) After the reaction, the reaction tube was taken out, the reaction solution was subjected to removal of the volatile solvent under reduced pressure, and purified by column chromatography to obtain trans-olefin.
The above process can be expressed by the following chemical equation:
in the above step, the metal catalyst is any one of cobalt iodide, cobalt bromide, cobalt chloride, cobalt acetate and cobalt acetylacetonate, wherein the metal catalyst is preferably cobalt iodide.
In the step of synthesizing the cis-olefin, the solvent is any one or more of methanol, ethanol, isopropanol, trifluoroethanol, acetonitrile, tetrahydrofuran, dioxane and toluene, wherein the preferable solvent is methanol.
In the synthesis step of the trans-olefin, the solvent is any one or more of acetonitrile, tetrahydrofuran, dioxane, toluene, N-dimethylformamide, disulfide sulfoxide and methanol, wherein the preferable solvent is acetonitrile.
In the synthesis step of the trans-olefin, the ligand is diphosphine ligand: dppe, dppm, dppp, dppb, dppf, dppn, XantPhos, rac-Binap, bis-nitrogen ligand: 1, 10-phen, monophosphine ligand: PPh3Wherein the preferred ligand is dppe.
In the above step, the reducing agent used is one or more of zinc powder, manganese powder, magnesium powder and iron powder of a metal simple substance, wherein the reducing agent is preferably zinc powder.
Compared with the prior art, the technical scheme adopted by the invention has the following advantages:
1. the method utilizes a strategy of adopting cheap transition metal cobalt for catalysis, takes water as a hydrogen source, and prepares the cis-form or trans-form olefin compound with high selectivity, thereby greatly reducing the production cost and having remarkable social benefit and economic benefit.
2. The invention has simple catalytic system, simple operation and good selectivity.
3. The invention can realize high-selectivity regulation and control of the configuration of a reaction product by adjusting the conditions of the ligand and the solvent under the catalysis of cobalt iodide.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to be limiting in any way, and any modifications or alterations based on the teachings of the present invention are intended to fall within the scope of the present invention.
The olefin synthesis method using water as a hydrogen source synthesizes olefin by taking alkyne as a synthesis raw material, cobalt compound as a catalyst and water as a hydrogen source through transfer hydrogenation.
The olefin synthesis method using water as a hydrogen source comprises a cis-olefin synthesis method and a trans-olefin synthesis method.
The method for synthesizing the cis-olefin comprises the following steps:
A. firstly, a cobalt compound, a reducing agent and internal alkyne are mixed according to a molar ratio of 1 (50-70): (10-30) sequentially adding the materials into a reaction container to obtain a material a;
B. and sequentially adding cobalt compounds into the material a according to a molar volume ratio (ml: mmol) of (100-300): the molar volume ratio (mu.l: mmol) of methanol to methanol of 1 is (3000-4000): 1, stirring and reacting at a constant temperature of 50-70 ℃, monitoring the reaction process by adopting TLC, removing the volatile solvent from the reaction solution under reduced pressure after the reaction is finished, and purifying by column chromatography to obtain the target cis-olefin.
The trans-olefin synthesis method comprises the following steps:
A. firstly, sequentially adding a cobalt compound and a ligand into a reaction container according to the molar ratio of 1 (1-1.5), and then adding the cobalt compound with the molar volume ratio (ml: mmol) of (50-150): 1, stirring the acetonitrile for 20-40 min until the acetonitrile is dissolved to obtain a material a;
B. and sequentially adding the materials a into the mixture in a molar ratio of 1: (50-70): (10-30) reducing agent and internal alkyne, and supplementing a cobalt compound with a molar volume ratio (ml: mmol) of (50-150): 1 to obtain a material b;
C. adding materials b into the mixture, wherein the molar volume ratio (mu l: mmol) of the materials b is (3000-4000): 1, stirring and reacting at a constant temperature of 50-70 ℃, monitoring the reaction process by adopting TLC, removing the volatile solvent from the reaction solution under reduced pressure after the reaction is finished, and purifying by column chromatography to obtain the target trans-olefin.
The cobalt compound is one or more of cobalt iodide, cobalt bromide, cobalt chloride, cobalt acetylacetonate and cobalt acetate.
The reducing agent is one or more of metal simple substance zinc powder, manganese powder, magnesium powder or iron powder.
The internal alkyne is diaryl internal alkyne, monoaryl fat internal alkyne, monoaryl internal alkyne ester or fat internal alkyne.
The ligand is dppe, dppm, dppp, dppb, dppf, dppn, XantPhos, rac-Binap, 1, 10-phen or PPh3。
The invention is further illustrated by the following specific examples:
example 1
In a glove box, cobalt iodide (0.01 mmol), zinc powder (0.6 mmol) and alkyne (0.2 mmol) are accurately weighed and loaded into a Schlenk reaction tube with a stirrer in sequence, a rubber plug is plugged, the glove box is removed, a syringe sucks 2ml of methanol, a microsyringe sucks 36 microliter (2 mmol) of water and adds the water into the reaction tube, the reaction tube is placed in a constant-temperature magnetic stirrer for stirring reaction at 60 ℃, and the reaction progress is monitored by TLC. After the reaction was completed, the reactor was opened and volatile materials were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as an eluent. The reaction solvent was concentrated under reduced pressure, followed by column chromatography purification to give a stilbene compound (99% yield, Z/E = 90: 10).1H NMR (400 MHz, CDCl3) δ 7.30 – 7.12 (m, 10H), 6.59 (s, 2H)。
Example 2
In a glove box, cobalt iodide (0.01 mmol), zinc powder (0.6 mmol) and alkyne (0.2 mmol) are accurately weighed and loaded into a Schlenk reaction tube with a stirrer in sequence, a rubber plug is plugged, the glove box is removed, a syringe sucks 2ml of methanol, a microsyringe sucks 36 microliter (2 mmol) of water and adds the water into the reaction tube, the reaction tube is placed in a constant-temperature magnetic stirrer for stirring reaction at 60 ℃, and the reaction progress is monitored by TLC. After the reaction was completed, the reactor was opened and volatile materials were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as an eluent. The reaction solvent was concentrated under reduced pressure, followed by column chromatography purification to give a stilbene compound (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)。
Example 3
In a glove box, cobalt iodide (0.01 mmol), zinc powder (0.6 mmol) and alkyne (0.2 mmol) are accurately weighed and loaded into a Schlenk reaction tube with a stirrer in sequence, a rubber plug is plugged, the glove box is removed, a syringe sucks 2ml of methanol, a microsyringe sucks 36 microliter (2 mmol) of water and adds the water into the reaction tube, the reaction tube is placed in a constant-temperature magnetic stirrer for stirring reaction at 60 ℃, and the reaction progress is monitored by TLC. After the reaction was completed, the reactor was opened and volatile materials were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as an eluent. The reaction solvent was concentrated under reduced pressure, followed by column chromatography purification to give a stilbene compound (98% yiel)d, 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)。
Example 4
In a glove box, cobalt iodide (0.01 mmol) and dppe (0.012 mmol) are accurately weighed and loaded into a Schlenk reaction tube with a stirrer, 1mL of acetonitrile is added for dissolution, and then the mixture is placed in a magnetic stirrer for stirring for 30min at normal temperature, so that the complexation is fully performed. Then accurately weighing zinc powder (0.6 mmol) and the above internal alkyne (0.2 mmol) to be sequentially added into the reaction tube, adding 1mL of acetonitrile, plugging a rubber plug and moving out of the glove box. The microsyringe sucks 36. mu.L (2 mmol) of water and adds the water into the reaction tube, the reaction tube is placed in a constant-temperature magnetic stirrer and stirred at 60 ℃, and the progress of the reaction is monitored by TLC. After the reaction was completed, the reactor was opened and volatile materials were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as an eluent. The reaction solvent was concentrated under reduced pressure, followed by column chromatography purification to give a stilbene compound (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)。
Example 5
In a glove box, cobalt iodide (0.01 mmol) and dppe (0.012 mmol) are accurately weighed and loaded into a Schlenk reaction tube with a stirrer, 1mL of acetonitrile is added for dissolution, and then the mixture is placed in a magnetic stirrer for stirring for 30min at normal temperature, so that the complexation is fully performed. Then accurately weighing zinc powder (0.6 mmol) and the above internal alkyne (0.2 mmol), sequentially adding into the reaction tube, and supplementing1mL acetonitrile, plug the plug and remove the glove box. The microsyringe sucks 36. mu.L (2 mmol) of water and adds the water into the reaction tube, the reaction tube is placed in a constant-temperature magnetic stirrer and stirred at 60 ℃, and the progress of the reaction is monitored by TLC. After the reaction was completed, the reactor was opened and volatile materials were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as an eluent. The reaction solvent was concentrated under reduced pressure, followed by column chromatography purification to give a stilbene compound (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)。
Example 6
In a glove box, cobalt iodide (0.01 mmol) and dppe (0.012 mmol) are accurately weighed and loaded into a Schlenk reaction tube with a stirrer, 1mL of acetonitrile is added for dissolution, and then the mixture is placed in a magnetic stirrer for stirring for 30min at normal temperature, so that the complexation is fully performed. Then accurately weighing zinc powder (0.6 mmol) and the above internal alkyne (0.2 mmol) to be sequentially added into the reaction tube, adding 1mL of acetonitrile, plugging a rubber plug and moving out of the glove box. The microsyringe sucks 36. mu.L (2 mmol) of water and adds the water into the reaction tube, the reaction tube is placed in a constant-temperature magnetic stirrer and stirred at 60 ℃, and the progress of the reaction is monitored by TLC. After the reaction was completed, the reactor was opened and volatile materials were removed under reduced pressure using a rotary evaporator, and purified by column chromatography using ethyl acetate and petroleum ether as an eluent. The reaction solvent was concentrated under reduced pressure, followed by column chromatography purification to give a stilbene compound (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 are merely illustrative of the technical idea and features of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention are included in the scope of the present invention.
Claims (1)
1. A method for synthesizing olefin by taking water as a hydrogen source is characterized in that diaryl internal alkyne is taken as a synthesis raw material, cobalt iodide is taken as a catalyst, water is taken as the hydrogen source, a reducing agent is metallic simple substance zinc powder, and olefin is synthesized by transfer hydrogenation reaction; the diaryl internal alkynes are:
、
or
(ii) a The olefin synthesis method comprises a cis-olefin synthesis method and a trans-olefin synthesis method; wherein:
the cis-olefin synthesis method comprises the following steps:
A. firstly, sequentially adding cobalt iodide, metal simple substance zinc powder and diaryl internal alkyne into a reaction container according to the molar ratio of 1: 50-70: 10-30 to obtain a material a;
B. sequentially adding methanol with the molar volume ratio of cobalt iodide of 100-300: 1 mL/mmol and water with the molar volume ratio of 3000-4000: 1 mu L/mmol into the material a, then stirring at a constant temperature of 50-70 ℃ for reaction, monitoring the reaction process by adopting TLC, removing a volatile solvent from a reaction solution under reduced pressure after the reaction is finished, and purifying by column chromatography to obtain a target cis-olefin;
the trans-olefin synthesis method comprises the following steps:
a1, sequentially adding cobalt iodide and a ligand dppe into a reaction container according to a molar ratio of 1: 1-1.5, adding acetonitrile with a molar volume ratio of cobalt iodide of 50-150: 1 mL/mmol, and stirring for 20-40 min until the mixture is dissolved to obtain a material a 1;
b1 and a material a1 are sequentially added with metal simple substance zinc powder and diaryl internal alkyne, wherein the molar ratio of the metal simple substance zinc powder to cobalt iodide is 1: 50-70: 10-30, and acetonitrile, the molar volume ratio of which to the diaryl internal alkyne is 50-150: 1 mL/mmol, is further added to obtain a material B;
c1 and the material b are added with water with a molar volume ratio of 3000-4000: 1 mu L/mmol, then the mixture is stirred at a constant temperature of 50-70 ℃ for reaction, the reaction process is monitored by adopting TLC, after the reaction is finished, the reaction solution is subjected to volatile solvent removal under reduced pressure, and the target trans-olefin is obtained through column chromatography purification.
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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 |
| 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 |
| CN113443952B (en) * | 2021-07-15 | 2022-11-04 | 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 |
| CN113563150B (en) * | 2021-07-15 | 2022-09-02 | 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 |
| 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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