CN115819388A - Preparation method of delta-cyclopentanolide - Google Patents
Preparation method of delta-cyclopentanolide Download PDFInfo
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- CN115819388A CN115819388A CN202111092891.4A CN202111092891A CN115819388A CN 115819388 A CN115819388 A CN 115819388A CN 202111092891 A CN202111092891 A CN 202111092891A CN 115819388 A CN115819388 A CN 115819388A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 66
- 229940043375 1,5-pentanediol Drugs 0.000 claims abstract description 30
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 21
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 23
- 238000005086 pumping Methods 0.000 description 13
- 239000012043 crude product Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- 238000004811 liquid chromatography Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000002347 injection Methods 0.000 description 8
- 239000007924 injection Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 6
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- -1 lactone compounds Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-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
- C07D309/18—Heterocyclic compounds containing six-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 containing only hydrogen and carbon atoms in addition to the ring hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/16—Heterocyclic compounds containing six-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
- C07D309/28—Heterocyclic compounds containing six-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 hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D309/30—Oxygen atoms, e.g. delta-lactones
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of organic synthesis, and provides a preparation method of delta-cyclopentanolide. Compared with the prior art that 1, 5-pentanediol and sodium hypochlorite aqueous solution are used as raw materials, dichloromethane is used as a solvent, and the delta-cyclopentanolide is prepared by reaction under the alkaline condition, the invention uses 1, 5-pentanediol and sodium hypochlorite as raw materials, uses 2, 6-tetramethylpiperidine oxide as an oxidation promoter, can obtain the delta-cyclopentanolide without organic solvent and alkaline condition, and is beneficial to environmental protection; meanwhile, 2, 6-tetramethyl piperidine oxide is fully contacted with 1, 5-pentanediol, so that the yield is improved; in addition, the microchannel reaction equipment has large reaction area, and the raw materials are fully contacted, thereby further improving the yield of the product. The examples show that: the preparation method provided by the invention has the advantages that the conversion rate of delta-cyclopentanolactone is 60.6-99.9%, the selectivity is 70.4-99.9%, and the yield is 99.80%.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of delta-cyclopentanolide.
Background
Delta-cyclopentanone (delta-valerolactone), also called tetrahydro-alpha-pyrone, is a light yellow or colorless aromatic liquid, can be well mixed and dissolved with organic solvents such as benzene, acetone, diethyl ether, ethanol and the like, is slightly soluble in water, and self-monomers are easy to undergo self-polymerization when standing, so that the requirement on storage is severe, such as addition of a proper amount of polymerization inhibitor or low-temperature storage.
The delta-cyclopentanolide is used as a very important pharmaceutical intermediate and organic intermediate raw material, and is easy to open ring and self polymerize; meanwhile, the polyester can also be polymerized with other lactone compounds such as caprolactone to obtain high molecular polyester with good plasticity, biodegradability, physiological activity, flexibility and extensibility; and the material is widely applied to the fields of environmental protection, medicine and liquid crystal materials. The preparation method of delta-valerolactone is mainly a pentanediol catalytic dehydrogenation method.
However, the catalytic dehydrogenation method of pentanediol is to obtain δ -cyclopentanolide by using 1, 5-pentanediol and an aqueous solution of sodium hypochlorite as raw materials and dichloromethane as a solvent and performing a reaction under alkaline conditions, but the yield is low.
Disclosure of Invention
In view of this, the present invention aims to provide a method for preparing δ -cyclopentanolide, wherein the yield of the preparation method provided by the present invention is 99.80%.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of delta-cyclopentanolide, which comprises the following steps:
taking 1, 5-pentanediol as a first material; a mixed solution of sodium hypochlorite, 2, 6-tetramethylpiperidine oxide and water as a second material;
and reacting the first material and the second material in a microchannel reaction device to obtain the delta-cyclopentanolide.
Preferably, the flow ratio of the first material to the second material is 1: (0.4-1.5).
Preferably, the flow ratio of the first material to the second material is 1: (0.6-1.2).
Preferably, the flow rate of the first material is 20-30 g/min.
Preferably, the mass ratio of the sodium hypochlorite to the 2, 6-tetramethylpiperidine oxide to the water in the second material is (2900-3750): (8-12): 1500.
preferably, the reaction temperature is-10-60 ℃ and the pressure is 0.01-0.5 MPa.
Preferably, the temperature of the reaction is 0-50 ℃, and the pressure is 0.05-0.3 MPa.
Preferably, the microchannel reaction device comprises a microchannel mixer and a microchannel reactor; the microchannel mixer is heart-shaped.
Preferably, the inner diameter of the microchannel reaction device is 0.01-0.018 mm.
The invention provides a preparation method of delta-cyclopentanolide, which comprises the following steps: taking 1, 5-pentanediol as a first material; a mixed solution of sodium hypochlorite, 2, 6-tetramethylpiperidine oxide and water as a second material; and reacting the first material and the second material in a microchannel reaction device to obtain the delta-cyclopentanolide. Compared with the prior art that 1, 5-pentanediol and sodium hypochlorite aqueous solution are used as raw materials, dichloromethane is used as a solvent, and the delta-cyclopentanolide is prepared by reaction under the alkaline condition, the invention uses 1, 5-pentanediol and sodium hypochlorite as raw materials, uses 2, 6-tetramethylpiperidine oxide as an oxidation promoter, can obtain the delta-cyclopentanolide without organic solvent and alkaline condition, and is beneficial to environmental protection; meanwhile, 2, 6-tetramethyl piperidine oxide is fully contacted with 1, 5-pentanediol, so that the yield is improved; in addition, the microchannel reaction equipment has large reaction area, and the raw materials are fully contacted, thereby further improving the yield of the product.
The data of the examples show that: the preparation method provided by the invention has the advantages that the conversion rate of delta-cyclopentanolactone is 60.6-99.9%, the selectivity is 70.4-99.9%, and the yield is 99.80%.
Drawings
FIG. 1 is a schematic diagram of a microchannel mixer;
FIG. 2 is a flow diagram for the preparation of delta-cyclopentanolide using a microchannel reaction apparatus.
Detailed Description
The invention provides a preparation method of delta-cyclopentanolide, which comprises the following steps:
taking 1, 5-pentanediol as a first material; a mixed solution of sodium hypochlorite, 2, 6-tetramethylpiperidine oxide (TEPMO) and water as a second material;
and reacting the first material and the second material in a microchannel reaction device to obtain the delta-cyclopentanolide.
In the present invention, the starting materials used in the present invention are preferably commercially available products unless otherwise specified.
In the present invention, the mass ratio of sodium hypochlorite, 2, 6-tetramethylpiperidine oxide (TEPMO) and water in the second material is preferably (2900 to 3750): (8-12): 1500, more preferably 3250: (8-12): 1500.
in the present invention, the flow ratio of the first material to the second material is preferably 1: (0.4 to 1.5), more preferably 1: (0.6 to 1.2), more preferably 1:1. in the present invention, the flow rate of the first material is preferably 20 to 30g/min.
In the present invention, the reaction temperature is preferably-10 to 60 ℃, and more preferably 0 to 50 ℃; the pressure is preferably 0.01 to 0.5MPa, and more preferably 0.05 to 0.3MPa.
In the present invention, the microchannel reactor apparatus includes a microchannel mixer and a microchannel reactor. In the present invention, the microchannel mixer is preferably of an love heart type, and the structure thereof is as shown in FIG. 1.
In the invention, the inner diameter of the microchannel reaction device is preferably 0.01-0.018 mm.
The reaction process of the first material and the second material in the microchannel reaction equipment is preferably as follows:
the first material and the second material respectively enter a microchannel mixer in the microchannel reaction equipment through two inlets for mixing, and then flow into the microchannel reactor for reaction. The reaction temperature and pressure defined above in the present invention are both conditions under which the reaction is carried out in a microchannel reactor.
After the reaction, the invention preferably further comprises the step of carrying out post-treatment on the obtained reaction liquid to obtain the delta-cyclopentanolide.
In the invention, the post-treatment preferably comprises standing and layering the obtained reaction feed liquid, and rectifying the obtained organic phase to obtain the delta-cyclopentanolide. The operation of the rectification is not particularly limited in the present invention, and may be an operation known to those skilled in the art.
FIG. 2 is a flow diagram for the preparation of delta-cyclopentanolide using a microchannel reaction apparatus.
The following examples are provided to illustrate the preparation of delta-cyclopentanolactone of the present invention in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Taking 1, 5-pentanediol as a first material, and taking TEPMO: the mass ratio of sodium hypochlorite to water is 10:3250:1500 of a mixture; pumping a first material and a second material into a micro-channel mixer through a pump for mixing, wherein the flow rates of the first material and the second material are both 20g/min; then the mixture enters a microchannel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃ at the moment, the mixture is reacted for 10min, reaction feed liquid in the microchannel reactor is extracted to be kept stand and layered, the obtained organic phase is rectified to obtain the crude product of the delta-cyclopentanolactone, 10mg of the crude product is added into 100mL of ethanol, and sample injection is carried out through liquid chromatography to obtain 9.98mg of the delta-cyclopentanolactone, 0.01mg of 1, 5-pentanediol, 0.01mg of a byproduct, the conversion rate is 10.37/10.38=99.90%, the selectivity is 9.98/9.99=99.9%, and the yield is 99.9% + 99.9% =99.80%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the microchannel mixer is shaped as a love heart.
Example 2
Taking 1, 5-pentanediol as a first material, taking a second material as TEPMO: the mass ratio of the sodium hypochlorite to the water is 8:3250:1500, pumping a first material and a second material into a microchannel mixer through a pump to mix, wherein the flow rates of the first material and the second material are both 20g/min, then feeding the materials into a microchannel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after the stable reaction is carried out for 10min, pumping reaction feed liquid in the microchannel reactor to stand and layer, rectifying the obtained organic phase to obtain the delta-cyclopentanolactone, adding 10mg of crude product into 100mL of ethanol, and carrying out liquid chromatography sample injection to obtain 7.32mg of the delta-cyclopentanolactone, 2.05mg of 1, 5-pentanediol, 0.62mg of a byproduct, the conversion rate of 8.26/10.31=80.1%, the selectivity of 7.32/7.94=92.2%, and the yield of 80.1% =92.2% =73.85%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the microchannel mixer is shaped as a love heart.
Example 3
Taking 1, 5-pentanediol as a first material, taking a second material as TEPMO: the mass ratio of sodium hypochlorite to water is 12:3250:1500, pumping a first material and a second material into a microchannel mixer through a pump to mix, wherein the flow rates of the first material and the second material are both 20g/min, then feeding the first material and the second material into a microchannel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after the reaction is stabilized for 10min, pumping reaction feed liquid in the microchannel reactor to stand and layer, rectifying the obtained organic phase to obtain the delta-cyclopentanolactone, adding 10mg of crude product into 100mL of ethanol, and performing liquid chromatography sample injection to obtain 6.85mg of the delta-cyclopentanolactone, 0.27mg of 1, 5-pentanediol, 2.88mg of a byproduct, the conversion rate of 10.12/10.39=97.4%, the selectivity of 6.85/9.73=70.4%, and the yield of 97.4% =70.4% =68.57%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is love heart type.
Example 4
Taking 1, 5-pentanediol as a first material, and taking a second material as TEPMO: the mass ratio of sodium hypochlorite to water is 10:3750:1500, pumping a first material and a second material into a microchannel mixer through a pump to mix, wherein the flow rates of the first material and the second material are both 20g/min, then feeding the materials into a microchannel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after reacting for 10min, pumping reaction feed liquid in the microchannel reactor to stand and layer, rectifying the obtained organic phase to obtain the delta-cyclopentanolide, adding 10mg of crude product into 100mL of ethanol, and feeding the crude product through liquid chromatography to obtain 7.45mg of the delta-cyclopentanolide, 1.66mg of 1, 5-pentanediol, 0.89mg of a byproduct, the conversion rate of 8.67/10.33=83.9%, the selectivity of 7.45/8.34=89.3%, and the yield of 83.9% =89.3% =74.9%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the microchannel mixer is shaped as a love heart.
Example 5
Taking 1, 5-pentanediol as a first material, taking a second material as TEPMO: the mass ratio of the sodium hypochlorite to the water is 10:2900:1500, pumping a first material and a second material into a microchannel mixer through a pump to mix, wherein the flow rates of the first material and the second material are both 20g/min, then feeding the first material and the second material into a microchannel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after reacting for 10min, pumping reaction feed liquid in the microchannel reactor to stand and layer, rectifying an obtained organic phase to obtain the delta-cyclopentanolactone, adding 10mg of crude product into 100mL of ethanol, and performing liquid chromatography sample injection to obtain 7.27mg of the delta-cyclopentanolactone, 2.54mg of 1, 5-pentanediol, 0.19mg of a byproduct, the conversion rate of 7.76/10.3=75.3%, the selectivity of 7.27/7.46=97.5%, and the yield of 75.3% =97.5% =73.42%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is love heart type.
Example 6
Taking 1, 5-pentanediol as a first material, and taking a second material as TEPMO: the mass ratio of sodium hypochlorite to water is 10:3250:1500g of mixture is pumped into a microchannel mixer by a pump to be mixed, the flow rates of the first material and the second material are both 20g/min, then the mixture enters a microchannel reactor with the temperature of 30 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 30 ℃, after the reaction is carried out for 10min, reaction feed liquid in the microchannel reactor is pumped to be kept stand and layered, the obtained organic phase is rectified to obtain the delta-cyclopentanolactone, 10mg of crude product is taken and added into 100mL of ethanol, and the delta-cyclopentanolactone 5.85mg,1, 5-pentanediol 2.73mg, the by-product 1.42mg, the conversion rate is 7.56/10.29=73.5%, and the selectivity is 5.85/7.27=80.5% can be obtained by liquid chromatography; the yield was 73.5% by 80.5% =59.17%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the microchannel mixer is shaped as a love heart.
Example 7
Taking 1, 5-pentanediol as a first material, taking a second material as TEPMO: the mass ratio of sodium hypochlorite to water is 10:3250:1500, pumping a first material and a second material into a microchannel mixer through a pump to mix, wherein the flow rates of the first material and the second material are both 20g/min, then feeding the first material and the second material into a microchannel reactor with the temperature of 0 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 0 ℃, after reacting for 10min, pumping reaction feed liquid in the microchannel reactor, standing and layering the reaction feed liquid, rectifying an obtained organic phase to obtain the delta-cyclopentanolactone, adding 10mg of crude product into 100mL of ethanol, and performing liquid chromatography sample injection to obtain 6.62mg of the delta-cyclopentanolactone, 1.53mg of 1, 5-pentanediol, 1.85mg of a byproduct, the conversion rate of 8.81/10.34=85.2%, the selectivity of 6.62/8.47=78.2%, and the yield of 85.2% =78.2% =66.63%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the microchannel mixer is shaped as a love heart.
Example 8
Taking 1, 5-pentanediol as a first material, taking a second material as TEPMO: the mass ratio of the sodium hypochlorite to the water is 10:3250:1500, pumping a first material and a second material into a microchannel mixer through a pump to mix, wherein the flow rates of the first material and the second material are both 30g/min, then feeding the first material and the second material into a microchannel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after reacting for 10min, pumping reaction feed liquid in the microchannel reactor to stand and layer, rectifying an obtained organic phase to obtain the delta-cyclopentanolactone, adding 10mg of crude product into 100mL of ethanol, and performing liquid chromatography sample injection to obtain 5.32mg of the delta-cyclopentanolactone, 4.03mg of 1, 5-pentanediol, 0.65mg of a byproduct, the conversion rate of 6.20/10.23=60.6%, the selectivity of 5.32/5.97=89.1%, and the yield of 60.6% =89.1% =54.0%; the inner diameter of a micro-channel in the micro-channel reaction equipment is 0.015mm; the microchannel mixer is shaped as a love heart.
Comparative example 1
Adding 1500g of 1, 5-pentanediol, 10g of TEPMO and 3250g of sodium hypochlorite into 1500g of water, mixing, stirring to fully mix, adding into a high-pressure reaction kettle, controlling the temperature at 10 ℃, reacting at constant temperature for 40 hours, standing and layering the reaction system, rectifying the obtained organic phase to obtain the delta-cyclopentanolide, wherein 850.3g of the prepared product can be collected, the conversion rate is 1104/1500=73.6%, the selectivity is 850.3/1061.55=80.1%, and the yield is 73.6% + 80.1% =58.95%.
Comparative example 2
The differences from example 1 are: the flow rate of the second material was 5g/min.
10mg of the crude product is added into 100mL of ethanol, and the delta-cyclopentanolide 4.01mg, the 1, 5-pentanediol 5.26mg, the byproduct 0.73mg, the conversion rate 4.93/10.19=48.4%, the selectivity 4.01/4.74=84.6% and the yield 48.4%. 84.6% =40.95% are obtained by liquid chromatography sample injection.
Comparative example 3
The differences from example 1 are: the flow rate of the second material was 35g/min.
10mg of the crude product is added into 100mL of ethanol, and sample injection is carried out by liquid chromatography to obtain 5.82mg of delta-cyclopentanolide, 1.07mg of 1, 5-pentanediol, 3.11mg of a byproduct, the conversion rate is 9.29/10.36=89.7%, the selectivity is 5.82/8.93=65.2%, and the yield is 89.7% by 65.2% =58.48%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The preparation method of delta-cyclopentanolide is characterized by comprising the following steps:
taking 1, 5-pentanediol as a first material; a mixed solution of sodium hypochlorite, 2, 6-tetramethylpiperidine oxide and water as a second material;
and reacting the first material and the second material in a microchannel reaction device to obtain the delta-cyclopentanolide.
2. The method of claim 1, wherein the flow ratio of the first material to the second material is 1: (0.4-1.5).
3. The method of claim 2, wherein the flow ratio of the first material to the second material is 1: (0.6-1.2).
4. The method according to claim 1, 2 or 3, wherein the flow rate of the first material is 20 to 30g/min.
5. The preparation method according to claim 1, wherein the mass ratio of the sodium hypochlorite to the 2, 6-tetramethylpiperidine oxide to the water in the second material is (2900-3750): (8-12): 1500.
6. the process according to claim 1, wherein the reaction is carried out at a temperature of-10 to 60 ℃ and a pressure of 0.01 to 0.5MPa.
7. The process according to claim 6, wherein the reaction temperature is 0 to 50 ℃ and the pressure is 0.05 to 0.3MPa.
8. The production method according to claim 1, wherein the microchannel reaction apparatus comprises a microchannel mixer and a microchannel reactor; the microchannel mixer is heart-shaped.
9. The production method according to claim 1 or 8, wherein the microchannel reaction apparatus has a microchannel inner diameter of 0.01 to 0.018mm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111092891.4A CN115819388B (en) | 2021-09-17 | 2021-09-17 | Preparation method of delta-cyclopentalactone |
| PCT/CN2021/139395 WO2023040101A1 (en) | 2021-09-17 | 2021-12-18 | METHOD FOR PREPARING δ-VALEROLACTONE |
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| CN202111092891.4A CN115819388B (en) | 2021-09-17 | 2021-09-17 | Preparation method of delta-cyclopentalactone |
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| JP3045194B2 (en) * | 1991-05-13 | 2000-05-29 | 日産化学工業株式会社 | Method for producing lactone derivative |
| US6222039B1 (en) * | 1998-07-13 | 2001-04-24 | Hoffman-La Roche Inc. | Process for the preparation of chiral lactones |
| JP2000038383A (en) * | 1998-07-23 | 2000-02-08 | Sumitomo Chem Co Ltd | Production of mevalolactone |
| DE50002160D1 (en) * | 1999-11-19 | 2003-06-18 | Ciba Sc Holding Ag | Process for the selective oxidation of alcohols using easily removable nitroxyl radicals |
| CN112961135B (en) * | 2021-02-05 | 2021-11-26 | 安庆奇创药业有限公司 | Method for continuously synthesizing benzyl substituted gluconolactone by adopting microchannel reaction device |
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| A. ABRAMOVICH ET AL.: "letter Organocatalytic Oxidative Dimerization of Alcohols to Esters", SYNLETT, vol. 23, pages 2261 * |
| PIER LUCIO ANELLI等: ""Oxidation of Diols with Alkali Hypochlorites Catalyzed by Oxammonium Salts under Two-Phase Conditions"", J. ORG. CHEM., vol. 54, no. 12, pages 2970 - 2972, XP055040329, DOI: 10.1021/jo00273a038 * |
| TOSHIFUMIKAGEYAMA等: "A facile oxidative lactonization of 1，w-diols with sodium bromite", CHEMISTRY LETTERS, pages 1097 - 1100 * |
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