CN111718246B - Method for synthesizing gamma-alkoxy alcohol - Google Patents
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Abstract
The invention provides a method for synthesizing gamma-alkoxy alcohol, which comprises the following steps: in the atmosphere of synthesis gas, under the action of a catalyst, an enol ether substrate sequentially undergoes hydroformylation and hydrogenation reactions, and a one-pot method is used for obtaining the gamma-alkoxy alcohol. The method has the main advantages that the synthetic route and the method are novel, the enol ether is creatively used as the raw material, the gamma-alkoxy alcohol is obtained in one step, and compared with other synthetic methods used at present, the method has obvious advantages; secondly, cobalt and alkyl phosphine with high hydrogenation activity are selected as catalyst ligands, lewis acid is selected as a carbonyl activating reagent, and the hydrogenation reaction activity of the system is further improved, so that the gamma-alkoxy alcohol is obtained by a one-pot method, the separation and purification of unstable intermediate gamma-alkoxy aldehyde are avoided, and the operation is simpler and safer.
Description
Technical Field
The invention belongs to the field of fine chemical engineering and coating, and particularly relates to a method for quickly and efficiently synthesizing gamma-alkoxy alcohol from an enol ether substrate.
Background
Gamma-alkoxy alcohols such as 3-methoxybutanol are very important solvents and synthetic intermediates. 3-methoxybutanol is a colorless transparent liquid, the density is 0.93g/mL, and the flash point is 46 ℃; because the normal pressure boiling point is up to 158-159 ℃, the 3-methoxy butanol is a very good high boiling point solvent and can be used for dissolving nitrocellulose paint, epoxy resin coating, brake oil viscosity regulator, printing ink and cutting oil. In nitrocellulose lacquers, 3-methoxybutanol can improve the paintability and flowability; while in alkyd coatings the paintability can be improved. The 3-methoxybutanol is matched with other solvents for use, and the drying time and the fluidity of the coating can achieve some special effects through the action of dissolving force. 3-Methoxybutanol can also be reacted with acetic anhydride to produce (3-methoxy) butyl acetate, which is also an excellent high boiling solvent (Ullmanns Encyclopedia of Industrial Chemistry: solvent, 2011).
At present, in the known literature reports, the main synthesis method of 3-methoxybutanol is to use crotonaldehyde and methanol as raw materials, add crotonaldehyde with methanol under the catalysis of alkali to obtain 3-methoxybutyraldehyde, and then obtain 3-methoxybutanol through hydrogenation reaction. Since the addition of methanol and crotonaldehyde is a reversible reaction, crotonaldehyde cannot be completely converted even if the amount of methanol is greatly excessive, and unreacted crotonaldehyde needs to be separated and recovered. Crotonaldehyde is active in chemical property, and is easy to generate side reactions such as self-condensation, dehydration and the like under the catalysis of alkali, so that the selectivity of addition reaction is about 80-90%, and more waste liquid is generated. The 3-methoxybutyraldehyde is active in chemical property, is very easy to generate reverse reaction, can remove methanol, and has high safety risk during operation. The hydrogenation of 3-methoxybutyraldehyde generally uses a nickel catalyst, and the temperature and pressure of the hydrogenation reaction are severe, thereby further limiting the wide application of the method. ( Xuke gao, organic chemical raw materials and intermediates for easy viewing: liaoning province petroleum chemical technology information general station, 1997 )
In conclusion, the 3-methoxybutanol is an excellent high-boiling point solvent, can be used as a solvent or a cosolvent of a coating, an ink and an adhesive, and has important economic value. The existing method for synthesizing gamma-alkoxy alcohol has the defects of general reaction selectivity, unstable intermediate separation and the like; therefore, there is a need to develop a new method for synthesizing γ -alkoxy alcohol.
Disclosure of Invention
The invention aims to provide a method for efficiently and quickly synthesizing gamma-alkoxy alcohol from an enol ether substrate, which takes cheap and easily obtained enol ether as a raw material to sequentially carry out hydroformylation and hydrogenation reactions, and obtains a gamma-alkoxy alcohol product with high yield and high selectivity by a one-pot method.
In order to achieve the purpose and achieve the technical effect, the invention adopts the following technical scheme:
a method for synthesizing a gamma-alkoxy alcohol: taking enol ether as a raw material, and obtaining a gamma-alkoxy alcohol product by a one-pot method in a synthetic gas atmosphere under the action of a catalyst.
Wherein the structural formula of the enol ether is as follows:
in the formula, R 1 、R 2 And R 3 Are respectively and independently selected from hydrogen, C1-C40 alkyl, alkenyl, alkynyl, ester group, carbonyl, amide group, phenyl, substituted phenyl, naphthyl, anthryl, phenanthryl or other aromatic ring and heteroaromatic substituent with higher carbon number.
Preferably, said R is 1 、R 2 And R 3 Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, cyclohexyl, phenyl and the like.
The reaction scheme is as follows:
in the present invention, the catalyst may be a heterogeneous or homogeneous hydroformylation catalyst, preferably a homogeneous catalyst; the catalyst consists of a metal and a ligand, can be prepared in advance, or can be prepared in situ in a reaction liquid by a metal precursor and the ligand, wherein the molar ratio of the metal to the ligand is 1:5 to 12.
In the present invention, the metal may be one or more of rhodium, cobalt, iridium, ruthenium, osmium, platinum and palladium, preferably cobalt and rhodium, and the metal is preferably used in a molar amount of 0.01 to 10.0mol%, preferably 0.01 to 2.0mol%, based on the molar amount of the enol ether substrate.
In the present invention, the rhodium or cobalt metal precursor may be, but is not limited to, co 2 (CO) 8 、Co(acac) 3 、Co(octanoate) 2 、[Rh(COD)Cl] 2 、[Rh(COD)OTf] 2 、[Rh(COD)BF 4 ] 2 、[Rh(COD)(acac)]、[Rh(CO) 2 (acac)]、[Rh(CO) 2 Cl] 2 One or more of (a).
In the present invention, the ligand may be, but is not limited to, one or more of phosphite, arylphosphine, alkylphosphine, arylarsenic, phosphoramidite ligands, preferably alkylphosphine ligands, and may be, but is not limited to, P (nBu) 3 、P(iBu) 3 、PCy 3 、PCyp 3 、P(nOct) 3 、Phobanes、Eicosyl phobane、2-Phosphabicyclo[3.3.1]nonanes, and the like.
In the present invention, a lewis acid promoter is further added to the reaction, the lewis acid promoter may be one or more of, but is not limited to, zinc chloride, zinc bromide, ferric chloride, ferric bromide, scandium trifluoromethanesulfonate, aluminum chloride, lithium chloride, etc., preferably one or more of zinc chloride, zinc bromide, and aluminum chloride, and the molar amount of the lewis acid promoter is 0.01 to 10.0mol%, preferably 0.01 to 2.0mol%, of the molar amount of the enol ether substrate.
In the present invention, the synthesis gas is a mixture of carbon monoxide and hydrogen, and the molar ratio of carbon monoxide to hydrogen is preferably 3 to 1;
in the present invention, the reaction pressure is 1.0 to 20.0MPa, preferably 10.0 to 13.0MPa; and/or the reaction temperature is 80-180 ℃, preferably 100-150 ℃; and/or the reaction time is 1 to 10 hours, preferably 3 to 6 hours.
In the present invention, the reaction solvent may be, but is not limited to, one or more of tetrahydrofuran, methyl tert-butyl ether, toluene, benzene, xylene, ethyl acetate, propyl acetate, ethanol, butanol, 3-methoxybutanol, and (3-methoxy) butyl acetate, and the amount of the solvent is 0.3 to 5.0 times, for example, 0.5 times, 1 time, 2 times, or 3 times the mass of the enol ether substrate.
In some preferred embodiments of the present invention, first, the metal precursor and the ligand are added into the solvent to perform coordination to prepare the catalyst solution, then the raw materials of the enol ether, the lewis acid catalyst and the solvent are added into the reaction device, the synthesis gas is charged, and the temperature is raised to the reaction temperature to perform the reaction.
By adopting the technical scheme, the invention has the following positive effects:
1. the enol ether substrate as the raw material is simple and easy to obtain, and the cost is low;
2. the catalyst consumption is less, the reaction selectivity is high, the product mainly comprises gamma-alkoxy alcohol, and only a small amount of hydrogenation byproducts are generated; adding Lewis acid to activate aldehyde carbonyl and promote hydrogenation reaction;
3. the preparation method can realize hydroformylation and hydrogenation reaction by a one-pot method, avoids the separation and purification of an unstable intermediate gamma-alkoxy aldehyde, and has simpler and safer operation.
Detailed Description
The present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples.
The main raw material information is as follows:
2-methoxypropene, 2-ethoxypropene, 1-ethoxypropene, 2-methoxy-1-butene, homemade, 98% (GC);
Co 2 (CO) 8 、Co(octanoate) 2 、[Rh(CO) 2 (acac)]、[Ir(COD)Cl] 2 annaiji chemistry;
P(nBu) 3 、P(iBu) 3 、PPh 3 、PCy 3 99% of an alatin reagent; p (nOct) 3 、RuCl 3 、PPh 3 ，J&A carbofuran reagent;
anhydrous tetrahydrofuran, toluene, methyl tert-butyl ether, diethyl ether, ethyl acetate, J & K carbofuran, AR;
zinc chloride, zinc bromide, aluminum chloride, lithium chloride, scandium trifluoromethanesulfonate Annaiji chemical, 98%.
The gas chromatography test conditions of the present invention are as follows:
the instrument model is as follows: agilent GC; a chromatographic column: agilent DB-5 (30 m.times.0.25 mm.times.0.25 μm); column temperature: the initial temperature is 40 ℃, the temperature is raised to 60 ℃ at 3 ℃/min, then the temperature is raised to 120 ℃ at 5 ℃/min, finally the temperature is raised to 180 ℃ at 10 ℃/min, and the temperature is kept for 3min; sample inlet temperature: 200 ℃; FID detector temperature: 300 ℃; split-flow sample injection, wherein the split-flow ratio is 40; sample injection amount: 2.0 mu L; h 2 Flow rate: 40mL/min; air flow rate: 400mL/min.
Example 1:
synthesis of 3-methoxybutanol by cobalt catalysis of 2-methoxypropene
In a glove box, sequentially adding [ Co ] 2 (CO) 8 ](0.28g,1.0mmol)、P(nBu) 3 (2.02g, 10.0 mmol) and tetrahydrofuran (20.0 g) were added to a single-neck flask equipped with a magnetic stirrer, stirring was turned on, and the metal precursor and formulation wereAfter the catalyst is dissolved and coordinated for 20 minutes, a catalyst solution is obtained, a single-port bottle is sealed, the single-port bottle is taken out of a glove box, the catalyst solution is pumped into an autoclave which is well replaced by nitrogen in advance by using a advection pump under the protection of nitrogen, then a tetrahydrofuran (30 g) solution of substrates 2-methoxypropene (144.2g, 2.0 mol) and zinc chloride (0.27g, 2.0 mmol) is added, finally a small amount of tetrahydrofuran (5 g) is fed, and residues in a feeding pipeline are flushed into a reaction kettle. After all the materials are added, replacing nitrogen with synthetic gas for three times, each time at 1.0MPa, and finally charging 13.0MPa of synthetic gas (CO: H) 2 = 1), starting autoclave stirring and jacket heat tracing, starting timing when the internal temperature of the reaction kettle reaches 150 ℃, keeping the temperature for reaction, continuously introducing synthesis gas in the reaction process, and keeping the reaction pressure stable. After 4 hours of reaction, a sample was taken and analyzed, and GC detection showed that the conversion of 2-methoxypropene was>99.5 percent, the selectivity of the product 3-methoxybutanol is 90.5 percent, and the byproduct is mainly 2-methoxypropane. HRMS-EIM + calcd for C5H12O2:104.0837,found 104.0839。
Example 2:
cobalt-catalyzed synthesis of 3-methoxybutanol from 2-methoxypropene
In a glove box, [ Co ] is sequentially mixed 2 (CO) 8 ](2.83g,10.0mmol)、P(nBu) 3 (4.05g, 20.0 mmol) and tetrahydrofuran (50.0 g) were charged into a single-neck flask equipped with a magnetic stirrer, stirring was turned on, and after dissolving and coordinating the metal precursor and ligand for 20 minutes, a catalyst solution was obtained, the single-neck flask was sealed, the catalyst solution was taken out of the glove box, the catalyst solution was pumped into an autoclave which had been previously replaced with nitrogen by a advective pump under nitrogen protection, followed by addition of a solution of 2-methoxypropene (144.2g, 2.0 mol), zinc chloride (0.27g, 2.0 mmol) in tetrahydrofuran (30 g), and finally a small amount of tetrahydrofuran (5 g), and the residue in the feed line was flushed into the reactor. After all the materials are added, replacing nitrogen with synthetic gas for three times, each time at 1.0MPa, and finally filling with 20.0MPa synthetic gas (CO: H) 2 = 1), starting autoclave stirring and jacket heat tracing, starting timing when the temperature in the reaction kettle reaches 80 ℃, keeping the temperature for reaction, continuously introducing synthesis gas in the reaction process, and keeping the reaction pressure stable. After 10 hours of reaction, sampling and analysis, GC detection showed 2The conversion of-methoxypropene was 59.6%, the selectivity to product 3-methoxybutanol was 86.2%, and the by-product was predominantly 2-methoxypropane.
Example 3:
synthesis of 3-methoxybutanol by cobalt catalysis of 2-methoxypropene
In a glove box, [ Co ] is sequentially mixed 2 (CO) 8 ](0.06g,0.2mmol)、P(nBu) 3 (0.61g, 1.5 mmol) and tetrahydrofuran (30.0 g) were added to a single-neck flask equipped with a magnetic stirrer, stirring was started, the metal precursor and ligand were dissolved and coordinated for 20 minutes to obtain a catalyst solution, the single-neck flask was sealed, the catalyst solution was taken out of the glove box, the catalyst solution was pumped into the autoclave by nitrogen displacement in advance by means of a advection pump under the protection of nitrogen, then a solution of 2-methoxypropene (144.2 g,2.0 mol), lithium chloride (1.70g, 40mmol) in tetrahydrofuran (40 g) was added, finally a small amount of tetrahydrofuran (5 g) was added, and the residue in the feed line was flushed into the reaction vessel. After all the materials are added, replacing nitrogen with synthetic gas for three times, each time at 1.0MPa, and finally filling with 6.0MPa synthetic gas (CO: H) 2 = 1), starting autoclave stirring and jacket heat tracing, starting timing when the temperature in the reaction kettle reaches 180 ℃, keeping the temperature for reaction, continuously introducing synthesis gas in the reaction process, and keeping the reaction pressure stable. After 10 hours of reaction, sampling analysis shows that GC detection shows that the conversion rate of 2-methoxypropene is 78.3%, the selectivity of the product 3-methoxybutanol is 89.1%, and the by-product is mainly 2-methoxypropane.
Example 4:
cobalt-catalyzed synthesis of 3-methoxybutanol from 2-methoxypropene
In the glove box, sequentially [ Co (octanoate) 2 ](0.35g,1.0mmol)、P(iBu) 3 (1.01g, 5.0 mmol) and methyl tert-butyl ether (40.0 g) were added to a single-neck flask equipped with a magnetic stirrer, stirring was turned on, the metal precursor and ligand were dissolved and coordinated for 20 minutes to obtain a catalyst solution, the single-neck flask was sealed, the catalyst solution was taken out of the glove box, the catalyst solution was pumped into an autoclave which had been previously replaced with nitrogen by a advection pump under nitrogen protection, then 2-methoxypropene (144.2g, 2.0 mol) and a methyl tert-butyl ether (30 g) solution of zinc bromide (0.45g, 2.0 mmol) were added, and finally, the mixture was fed againA small amount of methyl tert-butyl ether (5 g) was added and the residue in the feed line was flushed into the reactor. After all the materials are added, replacing nitrogen with synthetic gas for three times, each time at 1.0MPa, and finally filling 13.0MPa of synthetic gas (CO: H) 2 = 1), starting stirring of the high-pressure kettle and heat tracing of a jacket, starting timing when the temperature in the reaction kettle reaches 150 ℃, keeping the temperature for reaction, gathering synthesis gas in the reaction process, continuously introducing the synthesis gas, and keeping the reaction pressure stable. After 4 hours of reaction, sampling and analyzing, and GC detection shows that the conversion rate of the 2-methoxypropene is 98.9%, the selectivity of the product 3-methoxybutanol is 96.1%, and the byproduct is mainly 2-methoxypropane.
Example 5:
synthesis of 3-methoxybutanol by rhodium catalyzed 2-methoxypropene
In the glove box, sequentially combine [ Rh (CO) 2 (acac)](0.10g,0.4mmol)、P(nOct) 3 (0.74g, 2.0 mmol) and toluene (30.0 g) were added to a single-neck flask equipped with a magnetic stirrer, stirring was turned on, the metal precursor and ligand were dissolved and coordinated for 20 minutes to obtain a catalyst solution, the single-neck flask was sealed, the catalyst solution was discharged from the glove box, the catalyst solution was pumped into the autoclave by means of a advection pump under nitrogen protection, which had been previously replaced with nitrogen, followed by addition of a toluene (30 g) solution of 2-methoxypropene (144.2g, 2.0 mol), aluminum chloride (0.03g, 0.2mmol), and finally a small amount of toluene (10 g), and the residue in the feed line was flushed into the reaction vessel. After all the materials are added, replacing nitrogen with synthesis gas for three times, each time at 1.0MPa, and finally filling 8.0MPa synthesis gas (CO: H) 2 = 1), starting stirring of the high-pressure kettle and heat tracing of a jacket, starting timing when the temperature in the reaction kettle reaches 130 ℃, keeping the temperature for reaction, gathering synthesis gas in the reaction process, continuously introducing the synthesis gas, and keeping the reaction pressure stable. After 6 hours of reaction, sampling and analyzing, and GC detection shows that the conversion rate of the 2-methoxypropene is 98.4%, the selectivity of the product 3-methoxybutanol is 73.1%, and byproducts are mainly hydroformylation intermediates, namely 3-methoxybutyraldehyde and 2-methoxypropane. HRMS-EIM + calcd for C5H12O2:104.0837,found 104.0837。
Example 6:
synthesis of 3-ethoxy butanol from 2-ethoxy propylene by cobalt catalysis
In a glove box, sequentially adding [ Co ] 2 (CO) 8 ](0.28g,1.0mmol)、P(Bu) 3 (1.01g, 5.0mmol) and toluene (50 g) were charged in a single-neck flask equipped with a magnetic stirrer, stirring was started, and after dissolving and coordinating the metal precursor and the ligand for 20 minutes, a catalyst solution was obtained, the single-neck flask was sealed, the catalyst solution was taken out of the glove box, the catalyst solution was pumped into the autoclave which had been previously replaced with nitrogen by a advective pump under the protection of nitrogen, followed by addition of 2-ethoxypropene (172.3g, 2.0mol), a toluene solution (30 g) of lithium chloride (0.03g, 0.7mmol), and finally a small amount of toluene (5 g) was further fed, and the residue in the feed line was flushed into the reaction kettle. After all the materials are added, replacing nitrogen with synthetic gas for three times, each time at 1.0MPa, and finally filling 13.0MPa of synthetic gas (CO: H) 2 = 1), starting autoclave stirring and jacket heat tracing, starting timing when the internal temperature of the reaction kettle reaches 150 ℃, keeping the temperature for reaction, continuously introducing synthesis gas in the reaction process, and keeping the reaction pressure stable. After 5 hours of reaction, sampling and analyzing, GC detection shows that the conversion rate of the 2-methoxypropene is>99.5%, the selectivity of the product 3-ethoxybutanol is 93.1%, and the by-product is mainly 2-ethoxypropane. HRMS-EIM + calcd for C6H14O2:118.0994,found 118.0992。
Example 7:
synthesis of 3-ethoxy 2-methyl-1-propanol from 1-ethoxypropylene by cobalt catalysis
In a glove box, sequentially adding [ Co ] 2 (CO) 8 ](0.28g,1.0mmol)、P(Bu) 3 (1.01g, 5.0mmol) and toluene (40 g) were charged into a single-neck flask equipped with a magnetic stirrer, stirring was started, and after dissolving and coordinating the metal precursor and the ligand for 20 minutes, a catalyst solution was obtained, the single-neck flask was sealed, the catalyst solution was taken out of the glove box, the catalyst solution was pumped into the autoclave which had been previously replaced with nitrogen by a advective pump under the protection of nitrogen, followed by addition of 1-ethoxypropene (172.3g, 2.0mol), a toluene solution (30 g) of aluminum chloride (0.09g, 0.7mmol), and finally a small amount of toluene (5 g) was further fed, and the residue in the feed line was flushed into the reaction kettle. After all the materials are added, replacing nitrogen with synthetic gas for three times, each time at 1.0MPa, and finally filling with 5.0MPa synthetic gas (CO: H) 2 = 1), starting the autoclave for stirring and heating the jacket, and when the internal temperature of the autoclave reachesAnd when the temperature reaches 150 ℃, timing, keeping the temperature for reaction, summarizing the reaction process, continuously introducing the synthesis gas, and keeping the reaction pressure stable. After 5 hours of reaction, a sample was taken and analyzed, and GC detection showed that the conversion of 1-methoxypropene was>99.5 percent, the product is a mixture of 3-ethoxy-2-methyl-1-propanol and 2-ethoxy-1-butanol, the 2-ethoxy-1-butanol is taken as the main component, and the proportion of the two components is 31. HRMS-EIM + calcd for C6H14O2:118.0994,found 118.0994。
Example 8:
synthesis of 3-methoxy-1-pentanol from 2-methoxy-1-butene by cobalt catalysis
In a glove box, sequentially adding [ Co ] 2 (CO) 8 ](0.28g,1.0mmol)、P(Bu) 3 (1.01g, 5.0mmol) and diethyl ether (30 g) are added into a single-neck flask provided with a magnetic stirrer, stirring is started, a metal precursor and a ligand are dissolved and coordinated for 20 minutes to obtain a catalyst solution, the single-neck flask is sealed, the catalyst solution is taken out of a glove box, a advection pump is used for pumping the catalyst solution into an autoclave which is previously replaced by nitrogen under the protection of nitrogen, then 2-methoxy-1-butene (172.3g, 2.0mol) and an diethyl ether solution (30 g) of aluminum chloride (0.09g, 0.7mmol) are added, finally a small amount of diethyl ether (5 g) is added, and residues in a feeding pipeline are flushed into the reaction kettle. After all the materials are added, replacing nitrogen with synthetic gas for three times, each time at 1.0MPa, and finally charging 13.0MPa of synthetic gas (CO: H) 2 = 1), starting autoclave stirring and jacket heat tracing, starting timing when the internal temperature of the reaction kettle reaches 150 ℃, keeping the temperature for reaction, continuously introducing synthesis gas in the reaction process, and keeping the reaction pressure stable. After 5 hours of reaction, sampling and analyzing, GC detection shows that the conversion rate of the 2-methoxy-1-butene is>99.5%, the selectivity of the product 3-methoxy-1-pentanol is 95.6%, and the by-product is mainly 2-methoxybutane. HRMS-EIM + calcd for C6H14O2:118.0994,found 118.0995。
Example 9:
iridium-catalyzed synthesis of 3-methoxybutanol from 2-methoxypropene
In the glove box, [ Ir (COD) Cl] 2 (1.54g,2.3mmol)、PCy 3 (3.23g, 11.5 mmol) and ethyl acetate (20.0 g) were added to a single-neck flask equipped with a magnetic stirrer, the stirrer was turned on and gold was addedAfter the precursor and the ligand were dissolved and coordinated for 20 minutes, a catalyst solution was obtained, which was sealed in a single-neck flask, taken out of a glove box, and pumped into an autoclave previously purged with nitrogen by means of a advection pump under the protection of nitrogen, followed by addition of a solution of 2-methoxypropene (166.0 g,2.3 mol), a scandium trifluoromethanesulfonate (1.13g, 2.3mmol), and ethyl acetate (40 g), and finally a small amount of ethyl acetate (5 g) was fed, and the residue in the feed line was flushed into the reaction vessel. After all the materials are added, replacing nitrogen with synthesis gas for three times, each time at 1.0MPa, and finally filling 8.0MPa synthesis gas (CO: H) 2 = 1), starting autoclave stirring and jacket heat tracing, starting timing when the temperature in the reaction kettle reaches 110 ℃, keeping the temperature for reaction, continuously introducing synthesis gas in the reaction process, and keeping the reaction pressure stable. After 4 hours of reaction, sampling and analyzing, and GC detection shows that the conversion rate of the 2-methoxypropene is 35.7%, the selectivity of the product 3-methoxybutanol is 87.4%, and the by-product is mainly 3-methoxybutyraldehyde. HRMS-EIM + calcd for C5H12O2:104.0837,found 104.0837。
Example 10:
ruthenium-catalyzed synthesis of 3-methoxybutanol from 2-methoxypropene
In a glove box, ruCl is sequentially added 3 (0.70g,1.0mmol)、PPh 3 (1.46g, 5.2 mmol) and methyl tert-butyl ether (20.0 g) were added to a single-neck flask equipped with a magnetic stirrer, stirring was started, and after dissolving and coordinating the metal precursor and the ligand for 20 minutes, the catalyst solution was obtained, the single-neck flask was sealed, taken out of a glove box, the catalyst solution was pumped into an autoclave which had been previously replaced with nitrogen by a advection pump under nitrogen protection, and then the substrates 2-methoxypropene (150.0 g,2.1 mol), lithium chloride (0.09g, 2.1 mmol) and methyl tert-butyl ether (50 g) were added, and finally a small amount of methyl tert-butyl ether (8 g) was fed, and the residue in the feed line was flushed into the reaction vessel. After all the materials are added, replacing nitrogen with synthesis gas for three times, each time at 1.0MPa, and finally filling 8.0MPa synthesis gas (CO: H) 2 = 1), starting autoclave stirring and jacket heat tracing, starting timing when the temperature in the reaction kettle reaches 110 ℃, keeping the temperature for reaction, continuously introducing synthesis gas in the reaction process, and keeping the reaction pressure stable. After 4 hours of reaction, samples were taken for analysisGC detection shows that the conversion rate of the 2-methoxypropene is 45.7%, the selectivity of the product 3-methoxybutanol is 92.1%, and the byproduct is mainly 2-methoxypropane. HRMS-EIM + calcd for C5H12O2:104.0837,found 104.0836。
Claims (12)
1. A method for synthesizing gamma-alkoxy alcohol, which is characterized in that the method comprises the following steps: taking enol ether as a raw material, and obtaining a gamma-alkoxy alcohol product in a one-pot method in a synthetic gas atmosphere under the action of a catalyst; the catalyst is a heterogeneous or homogeneous hydroformylation catalyst, and the molar ratio of metal to ligand in the catalyst is 1; the metal is selected from one or more of rhodium or cobalt; the ligand is selected from one or more of aryl phosphine or alkyl phosphine ligands, and a Lewis acid promoter is also added in the reaction;
the structural formula of the enol ether is as follows:
in the formula, R 1 、R 2 And R 3 Each independently selected from hydrogen or C1-C40 alkyl.
2. The synthetic method of claim 1 wherein R is 1 、R 2 And R 3 Hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl.
3. The synthetic method of claim 1 wherein the catalyst is a homogeneous catalyst; the molar ratio of the metal to the ligand in the catalyst is 1:5 to 12.
4. The synthesis process of claim 1, wherein the metal is used in a molar amount of 0.01 to 10.0mol% based on the molar amount of the enol ether substrate.
5. The synthesis method according to claim 4, wherein the molar amount of the metal is 0.01-2.0 mol% of the molar amount of the enol ether substrate.
6. The synthesis method according to claim 1, wherein the rhodium or cobalt metal precursor is selected from Co 2 (CO) 8 、Co(acac) 3 、Co(octanoate) 2 、[Rh(COD)Cl] 2 、[Rh(COD)OTf] 2 、[Rh(COD)BF 4 ] 2 、[Rh(COD)(acac)]、[Rh(CO) 2 (acac)]、[Rh(CO) 2 Cl] 2 One or more of (a).
7. The method of claim 1, wherein the ligand is an alkyl phosphine ligand selected from the group consisting of P (nBu) 3 、P(iBu) 3 、PCy 3 、PCyp 3 、P(nOct) 3 A ligand.
8. The synthesis method according to claim 1, wherein the Lewis acid promoter is selected from one or more of zinc chloride, zinc bromide, ferric chloride, ferric bromide, scandium trifluoromethanesulfonate, aluminum chloride and lithium chloride, and the molar amount of the Lewis acid promoter is 0.01-10.0 mol% of the molar amount of the 2-methoxypropene.
9. The synthesis method of claim 8, wherein the Lewis acid promoter is selected from one or more of zinc chloride, zinc bromide and aluminum chloride, and the molar amount of the Lewis acid promoter is 0.01-2.0 mol% of the molar amount of the 2-methoxypropene.
10. The synthesis method according to claim 1, wherein the synthesis gas is a mixed gas of carbon monoxide and hydrogen, and the molar ratio of the carbon monoxide to the hydrogen is 3.
11. The synthesis method according to claim 1, characterized in that the reaction pressure is 1.0-20.0 MPa; and/or the presence of a gas in the gas,
the reaction temperature is 80-180 ℃; and/or the presence of a gas in the gas,
the reaction time is 1 to 10 hours.
12. The synthesis method according to any one of claims 1 to 3, wherein the reaction solvent is one or more selected from tetrahydrofuran, methyl tert-butyl ether, toluene, benzene, xylene, ethyl acetate, propyl acetate, ethanol, butanol, 3-methoxybutanol and (3-methoxy) butyl acetate, and the amount of the solvent is 0.3 to 5.0 times of the mass of the enol ether substrate.
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