CN115819388B - Preparation method of delta-cyclopentalactone - Google Patents
Preparation method of delta-cyclopentalactone Download PDFInfo
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- CN115819388B CN115819388B CN202111092891.4A CN202111092891A CN115819388B CN 115819388 B CN115819388 B CN 115819388B CN 202111092891 A CN202111092891 A CN 202111092891A CN 115819388 B CN115819388 B CN 115819388B
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- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 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
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 8
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 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
- 239000012043 crude product Substances 0.000 description 11
- 239000006227 byproduct Substances 0.000 description 10
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- 238000004811 liquid chromatography Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000005086 pumping Methods 0.000 description 8
- 230000032798 delamination Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- 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
- 239000000047 product Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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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-cyclopentalactone. Compared with the method for preparing delta-cyclopentalactone by taking 1, 5-pentanediol and sodium hypochlorite aqueous solution as raw materials and dichloromethane as solvent and performing reaction under alkaline conditions in the prior art, the method provided by the invention has the advantages that the delta-cyclopentalactone can be obtained without organic solvent and alkaline conditions by taking the 1, 5-pentanediol and sodium hypochlorite as raw materials and taking the 2, 6-tetramethylpiperidine oxide as a co-oxidant, so that the environment is protected; meanwhile, the 2, 6-tetramethyl piperidine oxide is fully contacted with the 1, 5-pentanediol, so that the yield is improved; in addition, the reaction area of the micro-channel reaction equipment is large, raw materials are fully contacted, and the product yield is further improved. The examples show that: the conversion rate of delta-cyclopentalactone by the preparation method provided by the invention 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-cyclopentalactone.
Background
Delta-cyclopentanol (delta-valerolactone) is also called tetrahydro-alpha-pyrone, is a pale yellow or colorless aromatic liquid, can be well mixed with benzene, acetone, diethyl ether, ethanol and other organic solvents, is slightly soluble in water, and can easily undergo self-polymerization when standing, so that the storage requirement is strict, such as adding a proper amount of polymerization inhibitor or storing at low temperature.
Delta-cyclopentanol is used as a very important pharmaceutical intermediate and organic intermediate raw material, and is easy to open loop and self-polymerize; meanwhile, the polymer polyester with good plasticity, biodegradability, physiological activity, flexibility and extensibility can be obtained by polymerizing with other lactone compounds such as caprolactone; and the material is widely applied in the fields of environmental protection, medicine and liquid crystal materials. The delta-valerolactone preparation method mainly adopts a pentanediol catalytic dehydrogenation method.
However, in the pentanediol catalytic dehydrogenation method, 1, 5-pentanediol and a sodium hypochlorite aqueous solution are used as raw materials, methylene dichloride is used as a solvent, and the reaction is performed under alkaline conditions to obtain delta-cyclopentanol, but the yield is low.
Disclosure of Invention
In view of the above, the present invention aims to provide a preparation method of delta-cyclopentalactone, and 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-cyclopentalactone, 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 is used as a second material;
And (3) reacting the first material and the second material in micro-channel reaction equipment to obtain the delta-cyclopentalactone.
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 sodium hypochlorite, 2, 6-tetramethylpiperidine oxide and water in the second material is (2900-3750): (8-12): 1500.
Preferably, the temperature of the reaction is-10 to 60 ℃ and the pressure is 0.01 to 0.5MPa.
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 microchannel reaction device has a microchannel inner diameter of 0.01-0.018 mm.
The invention provides a preparation method of delta-cyclopentalactone, 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 is used as a second material; and (3) reacting the first material and the second material in micro-channel reaction equipment to obtain the delta-cyclopentalactone. Compared with the method for preparing delta-cyclopentalactone by taking 1, 5-pentanediol and sodium hypochlorite aqueous solution as raw materials and dichloromethane as solvent and performing reaction under alkaline conditions in the prior art, the method provided by the invention has the advantages that the delta-cyclopentalactone can be obtained without organic solvent and alkaline conditions by taking the 1, 5-pentanediol and sodium hypochlorite as raw materials and taking the 2, 6-tetramethylpiperidine oxide as a co-oxidant, so that the environment is protected; meanwhile, the 2, 6-tetramethyl piperidine oxide is fully contacted with the 1, 5-pentanediol, so that the yield is improved; in addition, the reaction area of the micro-channel reaction equipment is large, raw materials are fully contacted, and the product yield is further improved.
The data of the examples show that: the conversion rate of delta-cyclopentalactone by the preparation method provided by the invention 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 chart for the preparation of delta-cyclopentalactone using a microchannel reactor.
Detailed Description
The invention provides a preparation method of delta-cyclopentalactone, 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 is used as a second material;
And the first material and the second material react in micro-channel reaction equipment to obtain the delta-cyclopentalactone.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
In the invention, the mass ratio of the sodium hypochlorite, the 2, 6-tetramethylpiperidine oxide (TEPMO) and the water in the second material is preferably (2900-3750): (8-12): 1500, further 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 invention, the flow rate of the first material is preferably 20-30 g/min.
In the present invention, the temperature of the reaction is preferably-10 to 60 ℃, and more preferably 0 to 50 ℃; the pressure is preferably 0.01 to 0.5MPa, more preferably 0.05 to 0.3MPa.
In the present invention, the microchannel reaction apparatus includes a microchannel mixer and a microchannel reactor. In the present invention, the microchannel mixer is preferably an loving type, and the structure is shown in fig. 1.
In the present invention, the inner diameter of the micro-channel reaction apparatus is preferably 0.01 to 0.018mm.
The reaction process of the first material and the second material in the microchannel reaction equipment is particularly preferably as follows:
The first material and the second material respectively enter a micro-channel mixer in the micro-channel reaction equipment through two inlets to be mixed, and then flow into the micro-channel reactor to be reacted. The temperature and pressure of the reaction defined above in the present invention refer to the conditions under which the reaction is carried out in the microchannel reactor.
After the reaction, the invention preferably further comprises post-treating the obtained reaction liquid to obtain the delta-cyclopentalactone.
In the present invention, the post-treatment preferably includes standing and layering the obtained reaction liquid, and rectifying the obtained organic phase to obtain the delta-cyclopentalactone. The rectification operation is not particularly limited in the present invention, and may be performed by operations well known to those skilled in the art.
FIG. 2 is a flow chart for the preparation of delta-cyclopentalactone using a microchannel reactor.
The following is a detailed description of the preparation method of delta-cyclopentalactone provided by the present invention, with reference to examples, which are not to be construed as limiting the scope of the invention.
Example 1
1, 5-Pentanediol is taken as a first material, and TEPMO is taken as a second material: the mass ratio of sodium hypochlorite to water is 10:3250: 1500; pumping the first material and the second material into a micro-channel mixer by a pump for mixing, wherein the flow rates of the first material and the second material are 20g/min; then the mixture enters a micro-channel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃ at this moment, the reaction is carried out for 10min, then the reaction feed liquid in the micro-channel reactor is extracted for standing and layering, the obtained organic phase is rectified to obtain the delta-cyclopentalactone crude product, 10mg of the crude product is added into 100mL of ethanol, 9.98mg of delta-cyclopentalactone, 0.01mg of 1, 5-pentanediol and 0.01mg of byproduct are obtained through liquid chromatography, 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% =99.80%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Example 2
1, 5-Pentanediol is used as a first material, and a second material is TEPMO: the mass ratio of sodium hypochlorite to water is 8:3250:1500, pumping a first material and a second material into a micro-channel mixer by a pump to mix, wherein the flow rates of the first material and the second material are 20g/min, then, the first material and the second material enter the micro-channel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, the reaction is stabilized for 10min, then, the reaction liquid in the micro-channel reactor is pumped to carry out standing delamination, the obtained organic phase is rectified to obtain delta-cyclopentanol, 10mg of crude product is added into 100mL of ethanol, 7.32mg of delta-cyclopentanol, 2.05mg of 1, 5-pentanediol and 0.62mg of byproduct are obtained by liquid chromatography sample injection, the conversion rate is 8.26/10.31=80.1%, the selectivity is 7.32/7.94=92.2%, and the yield is 80.1% 92.2% =73.85%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Example 3
1, 5-Pentanediol is used as a first material, and a second material is TEPMO: the mass ratio of sodium hypochlorite to water is 12:3250:1500, pumping a first material and a second material into a micro-channel mixer by a pump to mix, wherein the flow rates of the first material and the second material are 20g/min, then, the first material and the second material enter the micro-channel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, the reaction is stabilized for 10min, then, the reaction liquid in the micro-channel reactor is pumped to carry out standing delamination, the obtained organic phase is rectified to obtain delta-cyclopentanol, 10mg of crude product is added into 100mL of ethanol, and the delta-cyclopentanol is obtained by liquid chromatography sample injection, 1, 5-pentanediol is 0.27mg, by-product is 2.88mg, the conversion rate is 10.12/10.39=97.4%, the selectivity is 6.85/9.73=70.4%, and the yield is 97.4% 70.4% =68.57%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Example 4
1, 5-Pentanediol is used as a first material, and a second material is TEPMO: the mass ratio of sodium hypochlorite to water is 10:3750:1500, pumping a first material and a second material into a micro-channel mixer by a pump to mix, wherein the flow rates of the first material and the second material are 20g/min, then, the first material and the second material enter the micro-channel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after the reaction is carried out for 10min, the reaction liquid in the micro-channel reactor is pumped to carry out standing delamination, the obtained organic phase is rectified to obtain delta-cyclopentanol, 10mg of crude product is added into 100mL of ethanol, 7.45mg of delta-cyclopentanol, 1, 5-pentanediol 1.66mg of byproduct is obtained by liquid chromatography, the conversion rate is 8.67/10.33=83.9%, the selectivity is 7.45/8.34=89.3%, and the yield is 83.9% 89.3% =74.9%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Example 5
1, 5-Pentanediol is used as a first material, and a second material is TEPMO: the mass ratio of sodium hypochlorite to water is 10:2900:1500, pumping a first material and a second material into a micro-channel mixer by a pump to mix, wherein the flow rates of the first material and the second material are 20g/min, then, the first material and the second material enter the micro-channel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after the reaction is carried out for 10min, the reaction liquid in the micro-channel reactor is pumped to carry out standing delamination, the obtained organic phase is rectified to obtain delta-cyclopentanol, 10mg of crude product is added into 100mL of ethanol, 7.27mg of delta-cyclopentanol, 2.54mg of 1, 5-pentanediol, 0.19mg of byproduct is obtained by liquid chromatography sample injection, the conversion rate is 7.76/10.3=75.3%, the selectivity is 7.27/7.46=97.5%, and the yield is 75.3×97.5% = 73.42%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Example 6
1, 5-Pentanediol is used as a first material, and a second material is TEPMO: the mass ratio of sodium hypochlorite to water is 10:3250:1500g of mixture, pumping a first material and a second material into a micro-channel mixer by a pump for mixing, wherein the flow rates of the first material and the second material are 20g/min, then, the mixture enters a micro-channel 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, the reaction liquid in the micro-channel reactor is pumped for standing and layering, the obtained organic phase is rectified to obtain delta-cyclopentanol, 10mg of crude product is added into 100mL of ethanol, 5.85mg of delta-cyclopentanol, 2.73mg of 1, 5-pentanediol and 1.42mg of byproduct are obtained by liquid chromatography sample injection, the conversion rate is 7.56/10.29=73.5%, and the selectivity is 5.85/7.27=80.5%; yield 73.5% ×80.5% = 59.17%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Example 7
1, 5-Pentanediol is used as a first material, and a second material is TEPMO: the mass ratio of sodium hypochlorite to water is 10:3250:1500, pumping a first material and a second material into a micro-channel mixer by a pump to mix, wherein the flow rates of the first material and the second material are 20g/min, then, the materials enter the micro-channel reactor with the temperature of 0 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 0 ℃, after the reaction is carried out for 10min, the reaction liquid in the micro-channel reactor is pumped, the reaction liquid is kept still and layered, the obtained organic phase is rectified to obtain delta-cyclopentanol, 10mg of crude product is added into 100mL of ethanol, 6.62mg of delta-cyclopentanol, 1.53mg of 1, 5-pentanediol and 1.85mg of byproducts are obtained by liquid chromatography, the conversion rate is 8.81/10.34=85.2%, the selectivity is 6.62/8.47=78.2%, and the yield is 85.2% 78.2% = 66.63%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Example 8
1, 5-Pentanediol is used as a first material, and a second material is TEPMO: the mass ratio of sodium hypochlorite to water is 10:3250:1500, pumping a first material and a second material into a micro-channel mixer by a pump to mix, wherein the flow rates of the first material and the second material are 30g/min, then, the materials enter the micro-channel reactor with the temperature of 10 ℃ and the pressure of 0.2MPa, the temperature of the reactor is 10 ℃, after the reaction is carried out for 10min, the reaction liquid in the micro-channel reactor is pumped to carry out standing delamination, the obtained organic phase is rectified to obtain delta-cyclopentanol, 10mg of crude product is added into 100mL of ethanol, 5.32mg of delta-cyclopentanol, 4.03mg of 1, 5-pentanediol and 0.65mg of byproduct are obtained by liquid chromatography sample injection, the conversion rate is 6.20/10.23=60.6%, the selectivity is 5.32/5.97=89.1%, and the yield is 60.6×89.1% =54.0%; the inner diameter of the micro-channel in the micro-channel reaction equipment is 0.015mm; the shape of the microchannel mixer is an loving heart type.
Comparative example 1
1500G of 1, 5-pentanediol, 10g TEPMO and 3250g of sodium hypochlorite are added into 1500g of water to be mixed, stirred to be fully mixed, the mixture is added into a high-pressure reaction kettle, the temperature is controlled at 10 ℃, the constant temperature reaction is carried out for 40 hours, the reaction system is subjected to standing delamination, the obtained organic phase is rectified to obtain the delta-cyclopentalactone, 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 percent, 80.1 percent= 58.95 percent.
Comparative example 2
The differences from example 1 are: the flow rate of the second material was 5g/min.
10Mg of the crude product was added to 100mL of ethanol, and the mixture was subjected to liquid chromatography to obtain 4.01mg of delta-cyclopentalactone, 5.26mg of 1, 5-pentanediol, 0.73mg of by-product, a conversion of 4.93/10.19=48.4%, a selectivity of 4.01/4.74=84.6%, and a yield of 48.4% by 84.6% by 40.95%.
Comparative example 3
The differences from example 1 are: the flow rate of the second material was 35g/min.
10Mg of the crude product was added to 100mL of ethanol, and the mixture was subjected to liquid chromatography to obtain 5.82mg of delta-cyclopentalactone, 1.07mg of 1, 5-pentanediol, 3.11mg of by-product, 9.29/10.36=89.7% conversion, 5.82/8.93=65.2% selectivity, and 89.7% yield of 65.2% =58.48%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (1)
1. A method for preparing delta-cyclopentalactone, comprising the steps of:
taking 1, 5-pentanediol as a first material; a mixed solution of sodium hypochlorite, 2, 6-tetramethylpiperidine oxide and water is used as a second material;
Reacting the first material and the second material in micro-channel reaction equipment to obtain delta-cyclopentalactone;
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;
the flow rate of the first material is 20g/min;
the flow rate of the second material is 20g/min;
the temperature of the reaction is 10 ℃ and the pressure is 0.2MPa;
the microchannel reaction device comprises a microchannel mixer and a microchannel reactor; the micro-channel mixer is loving;
The inner diameter of the micro-channel reaction equipment is 0.015mm.
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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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| CN111646963A (en) * | 2020-06-29 | 2020-09-11 | 张明 | Preparation method of-cyclopentanolide |
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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 |
| CN113121449A (en) * | 2021-04-01 | 2021-07-16 | 复旦大学 | Full continuous flow preparation method of 2-methyl-4-amino-5-aminomethyl pyrimidine |
| CN113200996B (en) * | 2021-04-08 | 2022-10-11 | 复旦大学 | Continuous flow synthesis method of valerate |
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2021
- 2021-09-17 CN CN202111092891.4A patent/CN115819388B/en active Active
- 2021-12-18 WO PCT/CN2021/139395 patent/WO2023040101A1/en unknown
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| CN111646963A (en) * | 2020-06-29 | 2020-09-11 | 张明 | Preparation method of-cyclopentanolide |
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| Title |
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| "Oxidation of Diols with Alkali Hypochlorites Catalyzed by Oxammonium Salts under Two-Phase Conditions";Pier Lucio Anelli等;J. Org. Chem.;第54卷(第12期);2970-2972 * |
| A facile oxidative lactonization of 1，w-diols with sodium bromite;ToshifumiKAGEYAMA等;Chemistry Letters;1097-1100 * |
| letter Organocatalytic Oxidative Dimerization of Alcohols to Esters;A. Abramovich et al.;SYNLETT;第23卷;2261–2265 * |
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