CN114685404A - Preparation method of 2, 3-dihydrofuran intermediate for preparing cyclopropanecarboxaldehyde - Google Patents
Preparation method of 2, 3-dihydrofuran intermediate for preparing cyclopropanecarboxaldehyde Download PDFInfo
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- CN114685404A CN114685404A CN202011563129.5A CN202011563129A CN114685404A CN 114685404 A CN114685404 A CN 114685404A CN 202011563129 A CN202011563129 A CN 202011563129A CN 114685404 A CN114685404 A CN 114685404A
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- dihydrofuran
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- triphenylphosphine
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- JKTCBAGSMQIFNL-UHFFFAOYSA-N 2,3-dihydrofuran Chemical compound C1CC=CO1 JKTCBAGSMQIFNL-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- JMYVMOUINOAAPA-UHFFFAOYSA-N cyclopropanecarbaldehyde Chemical compound O=CC1CC1 JMYVMOUINOAAPA-UHFFFAOYSA-N 0.000 title abstract description 6
- ARGCQEVBJHPOGB-UHFFFAOYSA-N 2,5-dihydrofuran Chemical compound C1OCC=C1 ARGCQEVBJHPOGB-UHFFFAOYSA-N 0.000 claims abstract description 104
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 77
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 38
- -1 alkali metal salt Chemical class 0.000 claims abstract description 32
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 24
- 239000003112 inhibitor Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 239000007789 gas Substances 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 34
- 230000008569 process Effects 0.000 claims description 25
- 229910001220 stainless steel Inorganic materials 0.000 claims description 19
- 239000010935 stainless steel Substances 0.000 claims description 19
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 18
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 18
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 150000001340 alkali metals Chemical group 0.000 claims description 9
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 8
- CKRZKMFTZCFYGB-UHFFFAOYSA-N N-phenylhydroxylamine Chemical compound ONC1=CC=CC=C1 CKRZKMFTZCFYGB-UHFFFAOYSA-N 0.000 claims description 6
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 claims description 6
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 claims description 2
- 150000004703 alkoxides Chemical group 0.000 claims description 2
- 239000007983 Tris buffer Substances 0.000 claims 2
- VFAHXTJRZRHGDN-UHFFFAOYSA-N [Ru].[C]=O Chemical compound [Ru].[C]=O VFAHXTJRZRHGDN-UHFFFAOYSA-N 0.000 claims 1
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- GNPXKHTZVDUNOY-UHFFFAOYSA-N oxomethylidenerhodium Chemical compound O=C=[Rh] GNPXKHTZVDUNOY-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 25
- 239000000047 product Substances 0.000 description 22
- 239000012295 chemical reaction liquid Substances 0.000 description 15
- 238000004817 gas chromatography Methods 0.000 description 15
- 238000004064 recycling Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000006317 isomerization reaction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- UREFKUKELTYZEO-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 UREFKUKELTYZEO-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- DDKMFOUTRRODRE-UHFFFAOYSA-N chloromethanone Chemical compound Cl[C]=O DDKMFOUTRRODRE-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- UVSDNCAZVSQJQA-UHFFFAOYSA-N 2-(7-ethyl-1h-indol-3-yl)ethanol Chemical compound CCC1=CC=CC2=C1NC=C2CCO UVSDNCAZVSQJQA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000004852 dihydrofuranyl group Chemical group O1C(CC=C1)* 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- QQZMDXUEROTLLD-UHFFFAOYSA-N rhodium;triphenylphosphane Chemical compound [Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QQZMDXUEROTLLD-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/28—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method of a 2, 3-dihydrofuran intermediate for preparing cyclopropanecarboxaldehyde, which comprises the step of introducing mixed gas of carbon monoxide and nitrogen to react in the presence of a rare metal catalyst, alkali metal salt, 2, 5-dihydrofuran and a polymerization inhibitor to obtain the 2, 3-dihydrofuran. The reaction selectivity is 90-95%, and the yield is more than 90%. The preparation method of 2, 3-dihydrofuran has the advantages of cheap and easily obtained raw materials, simple and convenient operation, high product purity and less three wastes, reduces the production cost and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a preparation method of a 2, 3-dihydrofuran intermediate for preparing cyclopropanecarboxaldehyde.
Background
The 2, 3-dihydrofuran is a colorless liquid, has a boiling point of 54-55 ℃, is an important intermediate in fine organic chemical engineering, has wide application, is suitable for organic synthetic solvents, electronic chemicals, special resins, synthetic perfumes and the like, can be used as an important raw material of medicinal chemicals such as 7-ethyl tryptophol, isotopolic acid and the like, and can also be used for synthesizing an important organic intermediate cyclopropanecarbaldehyde. The methods reported in the reaction at present include the following methods:
patent US 25562525 discloses a synthesis process for isomerizing 2, 5-dihydrofuran in the presence of an alkali metal salt or an alkali metal salt-alcohol to give 2, 3-dihydrofuran. The synthesis method has the following defects: the preparation process temperature is as high as 170-200 ℃, the reaction time is as long as 6-12 hours, and when the alkali metal salt is used alone to promote isomerization, the dosage of the alkali metal salt is as high as 13 percent (relative to the raw material 2, 5-dihydrofuran); when the alkali metal salt-alcohol is used, the alkali metal salt is prepared in situ in absolute ethyl alcohol or tertiary butyl alcohol by using an alkali metal simple substance, so that the method is very dangerous for putting a large amount of flammable and explosive active alkali metal into industrial production and has very high requirements on transportation and storage of the raw material alkali metal simple substance.
DE1248669 discloses a process for heterogeneously catalyzed isomerization of 2, 5-dihydrofuran to 2, 3-dihydrofuran using certain metal catalysts, such as palladium, platinum, cobalt, ruthenium and nickel, but with low yields of only 29 to 63%.
The present inventors have found that both of the above two production methods are liable to cause the reaction to produce a large amount of by-products, resulting in a low or unstable yield.
Based on the prior art, the development of a preparation method which has mild preparation conditions, is easy to implement industrially, is more environment-friendly, has less three wastes, is stable and realizes the isomerization of 2, 5-dihydrofuran into 2, 3-dihydrofuran with high yield is still desired in the industry.
Disclosure of Invention
The invention provides a preparation method of a 2, 3-dihydrofuran intermediate for preparing cyclopropanecarboxaldehyde, which has the advantages of cheap and easily-obtained raw materials, simple synthesis process, mild preparation conditions, high product selectivity and yield and less three wastes, reduces the production cost and is easy for industrialized implementation.
The invention realizes the purpose of the invention through the following technical scheme:
the invention provides a preparation method of 2, 3-dihydrofuran, which comprises the following steps: introducing mixed gas of carbon monoxide and nitrogen to react in the presence of rare metal catalyst, alkali metal salt, 2, 5-dihydrofuran and polymerization inhibitor to obtain 2, 3-dihydrofuran. The detailed flow chart is shown in fig. 1.
The invention provides a preparation method of 2, 3-dihydrofuran, which adopts 2, 5-dihydrofuran as a raw material, isomerizes to generate the 2, 3-dihydrofuran under the catalytic action of a rare metal catalyst, and adds a polymerization inhibitor to inhibit the generation of byproducts. The reaction selectivity is 90-95%, and the yield is more than 90%. The preparation method of the 2, 3-dihydrofuran has the advantages of cheap and easily obtained raw materials, simple and convenient operation, high product purity and less three wastes, reduces the production cost and is suitable for industrial production.
According to the preparation method of 2, 3-dihydrofuran provided by the invention, the rare metal catalyst is any one of or a mixture of carbonyl tri (triaryl phosphine) ruthenium and carbonyl tri (triaryl phosphine) rhodium in any proportion as a catalyst.
Preferably, the rare metal catalyst is any one or a mixture of carbonyl tris (triphenylphosphine) ruthenium and carbonyl tris (triphenylphosphine) rhodium in any proportion as a catalyst.
Preferably, the rare metal catalyst is any one of carbonyl chlorine hydride tri (triphenylphosphine) ruthenium and carbonyl chlorine hydride tri (triphenylphosphine) rhodium or a mixture of the two in any proportion.
According to the preparation method of 2, 3-dihydrofuran provided by the invention, the polymerization inhibitor is any one or any two or three of phenylhydroxylamine, N-isopropylhydroxylamine and diethylhydroxylamine.
Preferably, the polymerization inhibitor is diethylhydroxylamine.
According to the preparation method of 2, 3-dihydrofuran provided by the invention, the alkali metal salt is alkali metal alkoxide.
Preferably, the alkali metal salt is an alkali metal tertiary alkoxide.
Preferably, the alkali metal salt is an alkali metal tert-butoxide.
Preferably, the alkali metal salt is any one or a mixture of two of potassium tert-butoxide and sodium tert-butoxide in any proportion.
According to the preparation method of 2, 3-dihydrofuran, the feeding mass ratio of the rare metal catalyst to the 2, 5-dihydrofuran is 1: 600-1000.
Preferably, the mass ratio of the rare metal catalyst to the 2, 5-dihydrofuran is 1: 800-.
According to the preparation method of the 2, 3-dihydrofuran, the mass ratio of the polymerization inhibitor to the 2, 5-dihydrofuran is 1: 30-200.
Preferably, the mass ratio of the polymerization inhibitor to the 2, 5-dihydrofuran is 1: 50-100.
The volume ratio of the carbon monoxide to the nitrogen is 1: 1-10.
Preferably, the volume ratio of carbon monoxide to nitrogen used is 1: 3-6.
The reaction is carried out for 2.5-5h at 90-150 ℃ and 0.5-3 MPa.
Preferably, the reaction is carried out at 110-140 ℃ and 1.2-1.7MPa for 3-4 h.
Preferably, the reaction is carried out at 130 ℃ and a pressure of 1.2-1.7MPa for 3 h.
The invention provides a preparation method of 2, 3-dihydrofuran, wherein the reaction is carried out in a stainless steel high-pressure reaction kettle.
The invention provides a preparation method of 2, 3-dihydrofuran, which comprises the following steps: adding any one or a mixture of any two of carbonyl chlorine hydrogen tri (triphenylphosphine) ruthenium or carbonyl chlorine hydrogen tri (triphenylphosphine) rhodium as a rare metal catalyst in a stainless steel high-pressure reaction kettle in any proportion, adding any one or a mixture of any two of phenylhydroxylamine, N-isopropylhydroxylamine and diethylhydroxylamine as a polymerization inhibitor in the presence of any one or a mixture of any two of potassium tert-butoxide and sodium tert-butoxide in any proportion, introducing mixed gas of carbon monoxide and nitrogen, reacting for 2.5-5h at 90-150 ℃ and 0.5-3MPa to isomerize 2, 5-dihydrofuran to obtain 2, 3-dihydrofuran, wherein the feeding mass ratio of the rare metal catalyst to the 2, 5-dihydrofuran is 1:600-1000, the feeding mass ratio of the polymerization inhibitor to the 2, 5-dihydrofuran is 1:30-200, the reaction selectivity is 90-95%, and the product 2, 3-dihydrofuran with the purity of over 98% is obtained by rectification after the reaction is finished, and the yield is over 90%.
Compared with the prior art, the invention has the following beneficial effects:
according to the preparation method of 2, 3-dihydrofuran provided by the invention, the reaction selectivity is improved to 90-95%, and the yield is improved to more than 90%; the adopted raw materials are cheap and easy to obtain, the use is more convenient and safe, the synthesis process is simple and convenient, the preparation conditions are mild, and three wastes are less; the production cost is reduced, and the industrial implementation is easy.
Drawings
FIG. 1 is a flow chart of a process for preparing 2, 3-dihydrofuran.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following description.
The materials according to the invention are, unless otherwise specified, commercially available.
Example 1
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. And (4) heating to 130 ℃, keeping the pressure of the reaction kettle at 1.2MPa, and continuously stirring for reaction for 3 hours to finish the reaction. The selectivity of the reaction was 93.7% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, collecting 54-57 deg.C fraction to obtain 98.5% purity product 2, 3-dihydrofuran 18.3g, HRMS calcd for C4H6O[M+H]+70.0901, found 70.0231. The yield is 91.0%; collecting 0.6g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 2
The reaction process is as follows: 50mg (0.053mmol) of carbonyl chloride hydrogen tris (triphenylphosphine) ruthenium, 0.5g (4.45mmol) of 98% potassium tert-butoxide, 50g (0.715mol) of 98% 2, 5-dihydrofuran and 0.9g (8.43mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.3MPa, introducing carbon monoxide, pressurizing to 0.5MPa, and magnetically stirring. The temperature is raised to 130 ℃, and the pressure of the reaction kettle reaches 1.7 MPa. And reacting for 3 h. The selectivity of the reaction was 94.6% by gas chromatography.
And (3) post-treatment process: and (3) rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 46.6g of the product 2, 3-dihydrofuran with the purity of 98.2%, wherein the yield is 93.0%. Collecting 0.8g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 3
The reaction process is as follows: 40mg (0.042mmol) of 97% carbonylchlorohydridetris (triphenylphosphine) ruthenium, 0.5g (4.45mmol) of 98% sodium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. The temperature is raised to 140 ℃, and the pressure of the reaction kettle reaches 1.4 MPa. And reacting for 3 h. The selectivity of the reaction was 92.2% by gas chromatography.
And (3) post-treatment process: and (3) rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 17.4g of the product 2, 3-dihydrofuran with the purity of 98.1%, wherein the yield is 87.0%. Collecting 0.7g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 4
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. And (5) heating to 70 ℃, keeping stirring and reacting for 3 hours, wherein the pressure of the reaction kettle reaches 0.8 MPa. The selectivity of the reaction was 82.9% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 9.0g of the product 2, 3-dihydrofuran with the purity of 98.1 percent and the yield of 45.0 percent; 8.7g of fraction 2, 5-dihydrofuran at the temperature of 64-67 ℃ is collected and recycled for use.
Example 5
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. And (5) heating to 100 ℃, keeping stirring and reacting for 3 hours, wherein the pressure of the reaction kettle reaches 1.0 MPa. The selectivity of the reaction was 87.3% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain a product 2, 3-dihydrofuran with the purity of 98.2% of 12.58g and the yield of 62.9%; 5.4g of fraction 2, 5-dihydrofuran at the temperature of 64-67 ℃ is collected and recycled for use.
Example 6
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Displacing with nitrogen for three times, introducing nitrogen to pressurize to 0.2MPa, then introducing carbon monoxide to pressurize to 0.3MPa, and magnetically stirring. And (5) heating to 150 ℃, keeping the pressure of the reaction kettle at 1.6MPa, and continuously stirring for reaction for 3 hours to finish the reaction. The selectivity of the reaction was 85.1% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 16.72g of product 2, 3-dihydrofuran with the purity of 98.2%, wherein the yield is 83.6%; collecting 0.2g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 7
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. And (5) heating to 180 ℃, keeping stirring and reacting for 3 hours, wherein the pressure of the reaction kettle reaches 1.6 MPa. The selectivity of the reaction was 46.7% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 8.9g of product 2, 3-dihydrofuran with the purity of 98.2%, wherein the yield is 44.5%; collecting 0.2g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 8
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonyl hydrogen chloride tris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.26g (3.46mmol) of 98% N-isopropylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. And (4) heating to 130 ℃, keeping the pressure of the reaction kettle at 1.3MPa, and continuously stirring for reaction for 3 hours to finish the reaction. The selectivity of the reaction was 86.5% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 16.94g of product 2, 3-dihydrofuran with the purity of 98.2%, wherein the yield is 84.7%; collecting 0.3g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 9
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.38g (3.48mmol) of 90% phenylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. And (4) heating to 130 ℃, keeping the pressure of the reaction kettle at 1.3MPa, and continuously stirring for reaction for 3 hours to finish the reaction. The selectivity of the reaction was 83.1% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 16.08g of product 2, 3-dihydrofuran with the purity of 98.2%, wherein the yield is 80.4%; collecting 0.4g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 10
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing nitrogen for three times, replacing the reaction gas atmosphere with a mixed gas of carbon monoxide and nitrogen in a volume ratio of 1:2, and magnetically stirring. And (4) heating to 130 ℃, wherein the pressure of the reaction kettle reaches 0.2MPa, and stirring to react for 3 hours. The selectivity of the reaction was 75.7% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 4.2g of a product 2, 3-dihydrofuran with the purity of 98.5%, wherein the yield is 21.0%; collecting 13.9g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 11
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.8MPa, introducing carbon monoxide, pressurizing to 1.0MPa, and magnetically stirring. And (5) heating to 130 ℃, keeping stirring and reacting for 3 hours, wherein the pressure of the reaction kettle reaches 2.5 MPa. The selectivity of the reaction was 90.8% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 17.26g of product 2, 3-dihydrofuran with the purity of 98.5%, wherein the yield is 86.3%; collecting 0.6g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 12
The reaction process is as follows: 20mg (0.021mmol) of 97% carbonylchlorohydroxytris (triphenylphosphine) ruthenium, 0.2g (1.78mmol) of 98% potassium tert-butoxide, 20g (0.286mol) of 98% 2, 5-dihydrofuran and 0.3g (3.37mmol) of 98% diethylhydroxylamine were added in this order to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 1.8MPa, introducing carbon monoxide, pressurizing to 2.7MPa, and magnetically stirring. And (4) heating to 130 ℃, keeping stirring and reacting for 3 hours, wherein the pressure of the reaction kettle reaches 4.8 MPa. The selectivity of the reaction was 10.8% by gas chromatography.
And (3) post-treatment process: rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 2.02g of a product 2, 3-dihydrofuran with the purity of 98.5%, wherein the yield is 10.1%; collecting 0.2g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 13
The reaction process is as follows: 20mg (0.021mmol) of carbonyl chloride hydrogen tri (triphenylphosphine) ruthenium with the content of 97 percent and 20g (0.286mol) of 2, 5-dihydrofuran with the content of 98 percent are sequentially added into a stainless steel high-pressure reaction kettle. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. The temperature is raised to 130 ℃, and the pressure of the reaction kettle reaches 1.2 MPa. And reacting for 3 h. The selectivity of the reaction was 67.2% by gas chromatography.
And (3) post-treatment process: and (3) rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 10.2g of a product 2, 3-dihydrofuran with the purity of 98.1%, wherein the yield is 51%. Collecting 4.4g of fraction 2, 5-dihydrofuran at 64-67 ℃, and recycling and reusing.
Example 14
The reaction process is as follows: 0.2g (1.78mmol) of potassium tert-butoxide with a content of 98% and 20g (0.286mol) of 2, 5-dihydrofuran with a content of 98% are added in succession to a stainless steel autoclave. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. The temperature is raised to 130 ℃, and the pressure of the reaction kettle reaches 1.2 MPa. And reacting for 3 h. The selectivity of the reaction was 27.4% by gas chromatography.
And (3) post-treatment process: and (3) rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 3.82g of the product 2, 3-dihydrofuran with the purity of 98.0%, wherein the yield is 19.1%. 5.9g of fraction 2, 5-dihydrofuran at the temperature of 64-67 ℃ is collected and recycled for use.
Example 15
The reaction process is as follows: 20mg (0.021mmol) of carbonyl hydrogen chloride tri (triphenylphosphine) ruthenium with the content of 97%, 0.2g (1.78mmol) of potassium tert-butoxide with the content of 98% and 20g (0.286mol) of 2, 5-dihydrofuran with the content of 98% are added into a stainless steel high-pressure reaction kettle in sequence. Replacing with nitrogen for three times, introducing nitrogen, pressurizing to 0.2MPa, introducing carbon monoxide, pressurizing to 0.3MPa, and magnetically stirring. The temperature is raised to 130 ℃, and the pressure of the reaction kettle reaches 1.2 MPa. And reacting for 3 h. The selectivity of the reaction was 75.6% by gas chromatography.
And (3) post-treatment process: and (3) rectifying the reaction liquid, and collecting 54-57 ℃ fractions to obtain 12.74g of the product 2, 3-dihydrofuran with the purity of 98.3%, wherein the yield is 63.7%. 3.0g of fraction 2, 5-dihydrofuran at the temperature of 64-67 ℃ is collected and recycled for use.
Examples 1, 4-7 are summarized in Table 1 below with respect to selectivity and product 2, 3-dihydrofuran yield when other reaction conditions are the same, only the reaction temperature is different:
TABLE 1 Effect of reaction temperature on reaction Selectivity and yield
As is clear from table 1, if the reaction temperature is too low, the yield of the reaction decreases. If the reaction temperature is too high, the selectivity and yield of the reaction are reduced, and the number of by-products is increased. Therefore, the reaction temperature of the method is controlled to be 90-150 ℃.
Examples 1, 8-9 are summarized in Table 2 below with respect to selectivity and yield of 2, 3-dihydrofuran product when other reaction conditions were the same and only the polymerization inhibitor species was different:
TABLE 2 Effect of different polymerization inhibitors on reaction Selectivity and yield
| Examples | Polymerization inhibitor | Selectivity/%) | Yield/% |
| 1 | Diethylhydroxylamine | 93.7 | 91.0 |
| 8 | Isopropyl hydroxylamine | 86.5 | 84.7 |
| 9 | Phenylhydroxylamine compounds | 83.1 | 80.4 |
As is clear from Table 2, different polymerization inhibitors have different effects on the promotion of the reaction, and diethylhydroxylamine is preferred as the polymerization inhibitor for the reaction.
Examples 1, 10-12 are summarized in Table 3 below with respect to selectivity and product 2, 3-dihydrofuran yield when other reaction conditions were the same, only reaction pressure was different:
TABLE 3 influence of reaction pressure on reaction Selectivity and yield
| Examples | pressure/MPa | Selectivity/%) | Yield/% |
| 1 | 1.3 | 93.7 | 91.0 |
| 10 | 0.2 | 75.7 | 21.0 |
| 11 | 2.5 | 90.8 | 86.3 |
| 12 | 4.8 | 10.8 | 10.1 |
As is clear from Table 1, when the reaction pressure is too low or too high, the selectivity and yield of the reaction are remarkably lowered and the amount of by-products is increased, so that the reaction pressure is controlled to be 0.5 to 3 MPa.
Examples 1, 13-15 are summarized in Table 4 below with respect to selectivity and product 2, 3-dihydrofuran yield when other reaction conditions were the same and only the promoters (rare metal catalyst, alkali metal salt and polymerization inhibitor are collectively referred to herein as "promoters") were different:
TABLE 4 Effect of auxiliary Agents on reaction Selectivity and yield
As can be seen from Table 4, the selectivity and yield of the reaction were significantly improved by adding the polymerization inhibitor. Therefore, the method is a feasible preparation method of the 2, 3-dihydrofuran.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed. The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of 2, 3-dihydrofuran is characterized in that mixed gas of carbon monoxide and nitrogen is introduced to react in the presence of rare metal catalyst, alkali metal salt, 2, 5-dihydrofuran and polymerization inhibitor to obtain the 2, 3-dihydrofuran.
2. The method for preparing 2, 3-dihydrofuran according to claim 1, wherein the rare metal catalyst is any one of or a mixture of a tris (triarylphosphine) carbonyl ruthenium catalyst and a tris (triarylphosphine) carbonyl rhodium catalyst in any proportion;
preferably, the rare metal catalyst is any one or a mixture of carbonyl tris (triphenylphosphine) ruthenium and carbonyl tris (triphenylphosphine) rhodium in any proportion as a catalyst;
preferably, the rare metal catalyst is any one of carbonyl chlorine hydride tri (triphenylphosphine) ruthenium and carbonyl chlorine hydride tri (triphenylphosphine) rhodium or a mixture of the two in any proportion.
3. The method for preparing 2, 3-dihydrofuran according to claim 1 or 2, wherein the polymerization inhibitor is any one or a combination of any two or a combination of three of phenylhydroxylamine, N-isopropylhydroxylamine and diethylhydroxylamine;
preferably, the polymerization inhibitor is diethylhydroxylamine.
4. A process for producing 2, 3-dihydrofuran according to any one of claims 1 to 3, wherein the alkali metal salt is an alkali metal alkoxide;
preferably, the alkali metal salt is an alkali metal tertiary alkoxide;
preferably, the alkali metal salt is an alkali metal tert-butoxide;
preferably, the alkali metal salt is any one or a mixture of two of potassium tert-butoxide and sodium tert-butoxide in any proportion.
5. The method for preparing 2, 3-dihydrofuran according to any one of claims 1-4, wherein the mass ratio of the rare metal catalyst to the 2, 5-dihydrofuran is 1: 600-1000;
preferably, the mass ratio of the rare metal catalyst to the 2, 5-dihydrofuran is 1: 800-.
6. The method for preparing 2, 3-dihydrofuran according to any one of claims 1-5, wherein the mass ratio of the polymerization inhibitor to the 2, 5-dihydrofuran is 1: 30-200;
preferably, the mass ratio of the polymerization inhibitor to the 2, 5-dihydrofuran is 1: 50-100.
7. A process according to any one of claims 1 to 6, wherein the volume ratio of carbon monoxide to nitrogen is from 1:1 to 10;
preferably, the volume ratio of carbon monoxide to nitrogen used is 1: 3-6.
8. A process for the preparation of 2, 3-dihydrofuran according to any one of claims 1 to 7, wherein the reaction is carried out at 90 to 150 ℃ and a pressure of 0.5 to 3MPa for 2.5 to 5 h;
preferably, the reaction is carried out for 3-4h at the temperature of 110-140 ℃ and under the pressure of 1.2-1.7 MPa;
preferably, the reaction is carried out at 130 ℃ and a pressure of 1.2-1.7MPa for 3 h.
9. A process according to any one of claims 1 to 8, wherein the reaction is carried out in a stainless steel autoclave.
10. A process for the preparation of 2, 3-dihydrofuran according to any one of claims 1-9, wherein said process is: adding one of carbonyl chlorine hydride tri (triphenylphosphine) ruthenium or carbonyl chlorine hydride tri (triphenylphosphine) rhodium or a mixture of the two in any proportion into a stainless steel high-pressure reaction kettle as a rare metal catalyst, adding any one or any two or three of phenylhydroxylamine, N-isopropylhydroxylamine and diethylhydroxylamine as a polymerization inhibitor in the presence of any one or two of tert-butyl potassium alkoxide and tert-butyl sodium alkoxide in any proportion of a mixture, introducing a mixed gas of carbon monoxide and nitrogen gas, reacting for 2.5-5h at 90-150 ℃ and 0.5-3MPa to isomerize 2, 5-dihydrofuran to obtain 2, 3-dihydrofuran, the mass ratio of the rare metal catalyst to the 2, 5-dihydrofuran is 1:600-1000, the mass ratio of the polymerization inhibitor to the 2, 5-dihydrofuran is 1: 30-200.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2556325A (en) * | 1951-06-12 | Production of z | ||
| FR987542A (en) * | 1949-04-02 | 1951-08-14 | Rhone Poulenc Sa | Process for the isomerization of 2,5-dihydro furans |
| US5254701A (en) * | 1991-05-20 | 1993-10-19 | Eastman Kodak Company | Process for the production of mixtures of 2-hydroxytetrahydrofuran and 4-hydroxybutanal |
| CN1179154A (en) * | 1995-01-31 | 1998-04-15 | 伊斯曼化学公司 | Preparation of 2, 3 -dihydrofurans compounds |
| CN1223645A (en) * | 1996-05-03 | 1999-07-21 | 伊斯曼化学公司 | Continuous process for the conversion of 2,5-dihydrofuran to 2,3-dihydrofuran |
| CN102015670A (en) * | 2008-05-01 | 2011-04-13 | 可乐丽股份有限公司 | Method for producing vinyl ether compound |
-
2020
- 2020-12-25 CN CN202011563129.5A patent/CN114685404A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2556325A (en) * | 1951-06-12 | Production of z | ||
| FR987542A (en) * | 1949-04-02 | 1951-08-14 | Rhone Poulenc Sa | Process for the isomerization of 2,5-dihydro furans |
| US5254701A (en) * | 1991-05-20 | 1993-10-19 | Eastman Kodak Company | Process for the production of mixtures of 2-hydroxytetrahydrofuran and 4-hydroxybutanal |
| CN1179154A (en) * | 1995-01-31 | 1998-04-15 | 伊斯曼化学公司 | Preparation of 2, 3 -dihydrofurans compounds |
| CN1223645A (en) * | 1996-05-03 | 1999-07-21 | 伊斯曼化学公司 | Continuous process for the conversion of 2,5-dihydrofuran to 2,3-dihydrofuran |
| CN102015670A (en) * | 2008-05-01 | 2011-04-13 | 可乐丽股份有限公司 | Method for producing vinyl ether compound |
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