CN111646963B - Preparation method of delta-cyclopentanolide - Google Patents
Preparation method of delta-cyclopentanolide Download PDFInfo
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- CN111646963B CN111646963B CN202010609330.6A CN202010609330A CN111646963B CN 111646963 B CN111646963 B CN 111646963B CN 202010609330 A CN202010609330 A CN 202010609330A CN 111646963 B CN111646963 B CN 111646963B
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- hypochlorite
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- cyclopentanolide
- dichloromethane
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 86
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- 229940043375 1,5-pentanediol Drugs 0.000 claims abstract description 21
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 9
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 4
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000004321 preservation Methods 0.000 claims description 9
- 239000010410 layer Substances 0.000 claims description 8
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 7
- 239000012044 organic layer Substances 0.000 claims description 7
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- LWXVCCOAQYNXNX-UHFFFAOYSA-N lithium hypochlorite Chemical compound [Li+].Cl[O-] LWXVCCOAQYNXNX-UHFFFAOYSA-N 0.000 claims description 2
- SATVIFGJTRRDQU-UHFFFAOYSA-N potassium hypochlorite Chemical compound [K+].Cl[O-] SATVIFGJTRRDQU-UHFFFAOYSA-N 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 4
- 239000007792 gaseous phase Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract 1
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 4
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 229910052905 tridymite Inorganic materials 0.000 description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 coatings Substances 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 229910001504 inorganic chloride Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of delta-cyclopentanolide, which comprises the steps of taking 1, 5-pentanediol and hypochlorite aqueous solution as raw materials, taking dichloromethane as a solvent, and carrying out an oxidation reaction under an alkaline condition, wherein the reaction temperature of the oxidation reaction is 5-30 ℃, and the reaction time is 10-60 minutes; the concentration of the hypochlorite aqueous solution is 3-10%, and the feeding mode is dropwise adding; the alkaline reagent for generating alkaline condition in the reaction is selected from potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, pyridine and triethylamine. The preparation method of delta-cyclopentanolide provided by the invention can complete the reaction in a non-gaseous phase low-temperature environment, and the raw materials are cheap and easy to obtain, and the process is simple, thus being suitable for industrial production.
Description
Technical Field
The invention belongs to the field of chemical synthesis, and particularly relates to a preparation method of delta-cyclopentanolide.
Background
Delta-cyclopentanolactone (also called tetrahydro-alpha-pyrone) is an important organic intermediate raw material, is widely applied to the fields of medicines, coatings, adhesives and other fields, is produced by only American and German companies internationally at present, and the national demand mainly depends on import. The structure of delta-cyclopentanolactone is as follows:
at present, the literature reports that the preparation method of delta-cyclopentanolide is mainly obtained by performing Baeyer-Villiger oxidation reaction on cyclopentanone or performing dehydrogenation reaction on 1,5 pentanediol. Wherein, the cyclopentanone in the Baeyer-Villiger oxidation reaction is limited by petrochemical products and has narrow raw material source; and the use of peroxy acid in the reaction leads to great environmental protection pressure and is not beneficial to sustainable development, so the Baeyer-Villiger method for preparing valerolactone is not widely used in industry. The method for generating the delta-cyclopentanolide by taking the 1, 5-pentanediol as the raw material through oxidative dehydrogenation is widely applied to industrial production due to the advantages of simple method, mild reaction conditions, low cost and the like.
However, the existing methods for preparing delta-cyclopentanolide all require 1, 5-pentanediol to be completed under a specific high-temperature condition, and ensure that the reaction is a gas-phase dehydrogenation reaction, and if the temperature is lower, the reaction conversion rate is low.
For example, JP2012056927 discloses a method for producing delta-valerolactone by dehydrogenation of 1, 5-pentanediol, which uses a catalyst Cu/Al2O3 and needs to be completed at a higher temperature, in the disclosed example, the reaction temperature needs to be maintained at 260 ℃, and n-pentanoic acid is produced as a byproduct in the reaction product, which corrodes the reactor and makes the product separation difficult. US20110237806 discloses the same preparation method, which uses two stages of copper-based catalysts, the first stage catalyst is Cu-NaO/SiO2, the bed temperature is 300 ℃, the second stage catalyst is Cu-NaO-CaO/SiO2, the bed temperature is 260 ℃, and the reaction is carried out under normal pressure. In the disclosed examples, the conversion of 1, 5-pentanediol can reach 99%, and the delta-valerolactone selectivity is about 96%. CN103980241A also provides the same preparation method, except that the patent firstly carries out dehydration of 1, 5-pentanediol, obtains delta-valerolactone at a water content of less than 0.05 wt%, namely 500wppm, and then at 230-270 ℃ under the action of a dehydrogenation catalyst, wherein the dehydrogenation catalyst is a copper-based catalyst doped with Ag.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of delta-cyclopentanolide, which can complete the reaction in a non-gaseous phase low-temperature environment, and has the advantages of cheap and easily-obtained raw materials, simple process and suitability for industrial production.
The technical scheme adopted by the invention is as follows:
a preparation method of delta-cyclopentanolide takes 1, 5-pentanediol and hypochlorite aqueous solution as raw materials, takes methylene dichloride as a solvent, and carries out an oxidation reaction under an alkaline condition, wherein the reaction temperature of the oxidation reaction is 5-30 ℃.
The hypochlorite aqueous solution is selected from the group consisting of lithium hypochlorite, sodium hypochlorite, potassium hypochlorite, and calcium hypochlorite aqueous solutions. The aqueous hypochlorite solution may be selected from one of the above agents or a combination of a plurality of agents, preferably sodium hypochlorite and calcium hypochlorite.
The concentration of the aqueous hypochlorite solution is 3% to 10%, preferably 5%, and the preparation method of the aqueous hypochlorite solution adopts a method known in the art.
The alkaline reagent for generating alkaline condition in the above reaction is selected from potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, pyridine, and triethylamine. The alkaline agent may be selected from one of the above-mentioned agents, or may be selected from a combination of a plurality of the agents.
The feeding mode of the 1, 5-pentanediol, the hypochlorite aqueous solution, the dichloromethane and the alkaline reagent is as follows: firstly putting dichloromethane, alkaline reagent and 1, 5-pentanediol into a reaction vessel, and then slowly dropwise adding hypochlorite aqueous solution, wherein the temperature of the reaction vessel is controlled to be 5-30 ℃ all the time.
After the hypochlorite aqueous solution is dripped, the reaction is carried out for 10 to 60 minutes under the condition of heat preservation, and the reaction temperature of the heat preservation reaction is 5 to 30 ℃.
The mass ratio of the 1, 5-pentanediol to the hypochlorite aqueous solution to the dichloromethane to the alkaline reagent is 1:8-15: 5-10: 0.1-0.3.
The invention also provides a post-processing method: and after the oxidation reaction is finished, layering the reaction liquid, removing a water layer, concentrating dichloromethane in an organic layer at normal pressure, and continuously separating low-boiling-point substances such as dichloromethane and the like from the residual material by a rectifying tower to obtain the delta-cyclopentanolide.
The concentration temperature of the dichloromethane concentrated under normal pressure is 30-80 ℃.
Compared with the prior art, the invention provides a preparation method of delta-cyclopentanolide, which has the following beneficial effects:
1. the method adopts hypochlorite for oxidative dehydrogenation, the whole oxidation reaction is carried out in a non-gaseous phase low-temperature environment, the process condition is simpler and milder, the operation is more convenient, and the method has good industrialized conditions; the hypochlorite raw material is easy to obtain, the price is low, and the hypochlorite has good economic value.
2. The invention carries out post-treatment by a mode of concentrating first and then rectifying, and has the advantages of simple process, good purification effect, convenient operation and easy operation.
3. The method has the advantages of high reaction selectivity of hypochlorite oxidative dehydrogenation, convenient separation and treatment of byproduct inorganic chloride, easy batch production, higher product purity and higher yield. The total yield is more than or equal to 90 percent, and the GC purity is more than or equal to 99 percent. Not only solves the technical problem of low conversion rate of the 1, 5-pentanediol under the low temperature condition, but also has simple process, easy treatment of three wastes, good economic value and suitability for industrial production.
Detailed Description
The present invention is further described in the following description of the specific embodiments, which is not intended to limit the invention, but various modifications and improvements can be made by those skilled in the art based on the basic idea of the invention, but the scope of the invention is within the scope of the invention as long as they do not depart from the basic idea of the invention.
The various starting materials and reagents used in the examples of the present invention were all commercially available unless otherwise specified.
In the embodiment, the gas chromatography detection instrument and the method for the delta-cyclopentanolide comprise the following steps:
| instrument for measuring the position of a moving object | Gas chromatograph |
| Chromatographic column | KB-WAX 30m×0.53mm，0.5μm |
| Detector | FID |
| Column temperature | The initial temperature was 120 ℃ and held for 2 minutes; raising the temperature to 240 ℃ at a speed of 8 ℃/min, and keeping the temperature for 8 minutes |
| Sample introduction temperature | 260℃ |
| Detecting temperature | 280℃ |
| Carrier gas | Nitrogen 0.04MPa |
| Hydrogen gas | 0.15MPa |
| Air (W) | 0.15MPa |
| Sample volume | 0.1μL |
Example 1
1000kg of dichloromethane, 30kg of potassium carbonate and 100kg of 1, 5-pentanediol are sequentially added into a reaction vessel, the temperature is raised to 25 ℃, then 2500kg of 5% sodium hypochlorite aqueous solution is slowly dripped into the reaction vessel at the temperature of 25 ℃, and the reaction vessel is kept at the temperature of 25 ℃ for 35 minutes after dripping. And after the heat preservation is finished, the reaction liquid is separated, a water layer is removed, an organic layer is concentrated at 60 ℃ under normal pressure to obtain 975kg of dichloromethane, the remainder is continuously subjected to a rectifying tower to separate low-boiling-point substances such as 15kg of dichloromethane and the like to obtain 88kg of delta-cyclopentanolide, the total yield is 91%, and the GC purity of the delta-cyclopentanolide is 99.5% through detection.
Example 2
550kg of dichloromethane, 10kg of sodium hydroxide and 100kg of 1, 5-pentanediol are sequentially added into a reaction vessel, the reaction vessel is cooled to 10 ℃, 2600kg of 5% sodium hypochlorite aqueous solution is slowly dripped into the reaction vessel at the temperature of 10 ℃, and the temperature is kept for 10 minutes at 10 ℃ after the dripping is finished. And (3) after heat preservation is finished, layering the reaction liquid, removing a water layer, concentrating an organic layer at 45 ℃ under normal pressure to about 530kg of dichloromethane, continuously separating the rest materials through a rectifying tower to obtain low-boiling-point substances such as about 15kg of dichloromethane and the like to obtain 90kg of delta-cyclopentanolide, wherein the total yield is 93%, and the GC purity of the delta-cyclopentanolide is 99.6% through detection.
Example 3
750kg of dichloromethane, 20kg of calcium hydroxide and 100kg of 1, 5-pentanediol are sequentially added into a reaction vessel, the temperature is cooled to 5 ℃, 2800kg of 5% calcium hypochlorite aqueous solution is slowly dripped into the reaction vessel at the temperature of 8 ℃, and the temperature is kept for 45 minutes at the temperature of 5 ℃ after dripping. And (3) after heat preservation is finished, layering the reaction liquid, removing a water layer, concentrating an organic layer at 50 ℃ under normal pressure to obtain about 725kg of dichloromethane, continuously separating the rest materials through a rectifying tower to obtain low-boiling-point substances such as about 15kg of dichloromethane and the like to obtain 91kg of delta-cyclopentanolide, wherein the total yield is 95%, and the GC purity of the delta-cyclopentanolide is 99.8% through detection.
Example 4
550kg of dichloromethane, 20kg of pyridine and 100kg of 1, 5-pentanediol are sequentially added into a reaction vessel, the reaction vessel is cooled to 15 ℃, 3000kg of 5% calcium hypochlorite aqueous solution is slowly dripped into the reaction vessel at the temperature of 15 ℃, and the temperature is kept for 45 minutes at 15 ℃ after dripping. And (3) after heat preservation is finished, layering the reaction liquid, removing a water layer, concentrating an organic layer at 50 ℃ under normal pressure to about 530kg of dichloromethane, continuously separating the rest materials through a rectifying tower to obtain low-boiling-point substances such as about 15kg of dichloromethane and the like to obtain 86kg of delta-cyclopentanolide, wherein the total yield is 90%, and the GC purity of the delta-cyclopentanolide is 99.5% through detection.
Example 5
500kg of dichloromethane, 20kg of triethylamine and 100kg of 1, 5-pentanediol are sequentially added into a reaction vessel, the temperature is raised to 30 ℃, 2800kg of 5% sodium hypochlorite aqueous solution is slowly dripped at the temperature of 28 ℃, and the temperature is kept for 60 minutes at 30 ℃ after dripping. And (3) after the heat preservation is finished, layering the reaction liquid, removing a water layer, concentrating the organic layer at 50 ℃ under normal pressure to obtain 475kg of dichloromethane, continuously separating the rest materials through a rectifying tower to obtain low-boiling-point substances such as 15kg of dichloromethane and the like to obtain 90kg of delta-cyclopentanolide, wherein the total yield is 93%, and the GC purity of the delta-cyclopentanolide is 99.6% through detection.
It should be understood, however, that while the present invention has been described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (7)
1. A preparation method of delta-cyclopentanolide is characterized in that 1, 5-pentanediol and hypochlorite aqueous solution are used as raw materials, dichloromethane is used as a solvent, and an oxidation reaction is carried out under an alkaline condition, wherein the reaction temperature of the oxidation reaction is 5-30 ℃;
the feeding mode of the 1, 5-pentanediol, the hypochlorite aqueous solution, the dichloromethane and the alkaline reagent is as follows: firstly, putting dichloromethane, an alkaline reagent and 1, 5-pentanediol into a reaction vessel, and then slowly dropwise adding a hypochlorite aqueous solution, wherein the temperature of the reaction vessel is controlled to be 5-30 ℃ all the time;
after the hypochlorite aqueous solution is dripped, the reaction is carried out for 10 to 60 minutes under the condition of heat preservation, and the reaction temperature of the heat preservation reaction is 5 to 30 ℃.
2. The method for preparing delta-cyclopentanone, as claimed in claim 1, wherein the hypochlorite is selected from one or more of lithium hypochlorite, sodium hypochlorite, potassium hypochlorite, and calcium hypochlorite, and the concentration of the aqueous solution is 3% to 10%.
3. The method for preparing delta-cyclopentanolide, as claimed in claim 2, wherein the hypochlorite is sodium hypochlorite or calcium hypochlorite, and the concentration of the aqueous solution is 5%.
4. The method of claim 1, wherein the alkaline reagent for generating alkaline conditions in the reaction is selected from potassium carbonate, sodium bicarbonate, sodium hydroxide, potassium hydroxide, calcium hydroxide, pyridine, and triethylamine.
5. The preparation method of delta-cyclopentanolide as claimed in claim 4, wherein the mass ratio of 1, 5-pentanediol, the aqueous hypochlorite solution, dichloromethane, and the alkaline agent is 1:8-15: 5-10: 0.1-0.3.
6. The method for preparing delta-cyclopentanolide as claimed in claim 1, wherein after the oxidation reaction is completed, the reaction solution is separated into layers, the aqueous layer is discarded, the organic layer is first concentrated with dichloromethane at normal pressure, and the residue is further passed through a rectification column to separate out low-boiling-point substances, thereby obtaining delta-cyclopentanolide.
7. The method for preparing delta-cyclopentanolide according to claim 6, wherein the atmospheric concentration of dichloromethane is performed at a temperature of 30 to 80 ℃.
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| CN111646963A (en) | 2020-09-11 |
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