CN108794432B - Method for preparing gamma lactone by photosensitization catalysis - Google Patents
Method for preparing gamma lactone by photosensitization catalysis Download PDFInfo
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- CN108794432B CN108794432B CN201710291103.1A CN201710291103A CN108794432B CN 108794432 B CN108794432 B CN 108794432B CN 201710291103 A CN201710291103 A CN 201710291103A CN 108794432 B CN108794432 B CN 108794432B
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- 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
- C07D307/30—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 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
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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Abstract
The invention belongs to the technical field of spices, and particularly relates to a method for preparing gamma lactone by photosensitization catalysis. The invention takes acrylic acid or acrylic ester and normal alkanol as raw materials, takes a photosensitization catalyst and an auxiliary agent as catalysts, reacts under the irradiation of ultraviolet light to generate the propiolactone, and is rectified after the reaction is finished to obtain the pure propiolactone. The preparation method has higher yield, is beneficial to improving the productivity, and can reach 89.3 percent to the maximum; for the traditional process, the generation of waste acid and waste water is avoided; the addition of peroxide free radical initiator in the traditional process is avoided, and the method is safe and controllable compared with the traditional process.
Description
Technical Field
The invention belongs to the technical field of spices, and particularly relates to a method for preparing gamma lactone by photosensitization catalysis.
Background
The gamma lactone is a lactone series spice with higher value in the field of essence and spice, and is widely applied to the industries of food industry, daily use chemicals, health care and medical care and the like due to low threshold value and good photo-thermal stability and fat solubility.
The main synthesis process of the allene lactone is divided into two types, the first type is an olefine acid sulfuric acid catalytic cyclization process, and the representative industrial production process is a process for preparing peach aldehyde by undecylenic acid through sulfuric acid catalysis; the second type is the free radical addition process of normal alkanol and acrylic acid or methyl acrylate (such as CN101402628A, CN102838569B), and the representative process is the preparation of peach aldehyde and coconut aldehyde by acrylic acid or methyl acrylate and n-octanol and n-hexanol. At present, the two processes are mainly adopted in industrial mass production according to the advantages of raw material sources.
The propyl lactone process has low yield and serious three-waste pollution. The first type of process uses sulfuric acid in about 50-60% yield. The process generates a large amount of waste acid water, and the organic waste is high. The second kind of process has the same yield of only 65-75%, and a large amount of organic waste needs to be treated, thus polluting the environment. The optimal reaction temperature is 180 ℃, the normal alkanol/acrylic acid (methyl ester) is about 6-8 in the reaction process, a large amount of normal alkanol is recycled, and the energy consumption is high. In recent years, methods for preparing lactones by using solid supported catalysts have been developed, for example, the perilin of the university of combined fertilizer industry provides gamma-Al2O3A method for catalytically synthesizing gamma-undecalactone by using a supported Pd-Ni bimetallic catalyst is disclosed, wherein an impregnation method is adopted in the method for preparing gamma-Al2O3The supported Pd-Ni bimetallic catalyst contains noble metal, which increases the production cost to some extent.
Therefore, the development of a green and efficient process with convenient operation and high yield to prepare the propiolactone is of great significance.
Disclosure of Invention
The invention aims to overcome the technical problems of low product yield and large environmental pollution in the prior art, and provides a method for preparing propiolactone by photosensitization catalysis.
The invention realizes the aim through the following technical scheme, a method for preparing the propiolactone by photosensitization catalysis takes acrylic acid or acrylic ester and normal alkanol as raw materials, takes a photosensitization catalyst and an auxiliary agent as catalysts, generates the propiolactone by reaction under the irradiation of ultraviolet light, and then carries out rectification to obtain the pure propiolactone;
the reaction formula is shown as the formula (1):
preferably, the R substituents in the reaction formula are independently selected from H, CH3Or C2H5Any one of them;
preferably, n in the reaction formula is independently selected from any one of 2, 3, 4, 5, 6, 7 or 8;
the photosensitization catalyst is any one of 5,10,15, 20-tetraphenylporphyrin, 5,10,15, 20-tetraphenylmanganoporphyrin, 5,10,15, 20-tetraphenylzinc porphyrin, Bengal red, tris (2,2' -bipyridyl) ruthenium chloride, tris (2,2' -bipyridyl) ruthenium bis (hexafluorophosphate) salt or rose bengal B, and preferably tris (2,2' -bipyridyl) ruthenium chloride;
the auxiliary agent is quinuclidine, namely 1-azabicyclo [2.2.2] octane;
the method for preparing the propiolactone by the photosensitization catalysis has the further technical scheme that in the preparation method, the molar ratio of the propionic acid or the propionate to the normal alkanol is 1: (1-10), preferably 1: 1;
the method for preparing the gamma lactone by the photosensitization catalysis has the further technical scheme that in the preparation method, the use amount of the photosensitization catalyst is 0.1-10 percent, and the optimal amount is 0.1 percent of the molar amount of acrylic acid or propionate;
the method for preparing the gamma lactone by the photosensitization catalysis has the further technical scheme that in the preparation method, the molar ratio of the photosensitization catalyst to an auxiliary agent quinuclidine is 1: (0.1-10), and the optimal ratio is 1: 1;
the method for preparing the propiolactone by the photosensitization catalysis has the further technical scheme that in the preparation method, the reaction temperature is 0-60 ℃, the optimal reaction temperature is 10-40 ℃, and the further optimal reaction temperature is 25 ℃;
the invention adopts photosensitization catalysis to prepare the gamma lactone, provides the best choice for replacing the traditional process, and the process directly adds the photosensitization catalyst and the auxiliary agent and utilizes illumination to realize free radical addition ring combination.
Compared with the prior art, the invention has the following advantages:
1) the preparation method has higher yield, is beneficial to improving the productivity, and can reach 89.3 percent to the maximum;
2) compared with the traditional process, the invention avoids the generation of waste acid and waste water;
3) the invention avoids adding peroxide free radical initiator in the traditional process, and is safe and controllable compared with the traditional process;
4) compared with the traditional high-temperature process, the illumination reaction has milder conditions and lower energy consumption.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
Example 1
(1) Adding 72.1g (1.0mol) of acrylic acid and 130.2g (1mol) of n-octanol into a photosensitization reactor, and heating to 40 ℃;
(2) adding 0.6g (1mmol) of photosensitization catalyst 5,10,15, 20-tetraphenylporphyrin and 0.1g (-1 mmol) of auxiliary agent quinuclidine, irradiating by 15w of ultraviolet lamp, and reacting at 40 ℃;
(3) after the reaction is finished, 151.7g of peach aldehyde is obtained by rectification separation (the rectification pressure is 30Pa, the kettle temperature is 160 ℃, the tower top temperature is 121 ℃, and the GC content is more than or equal to 98.5%), and the yield is 82.3%.
Example 2
(1) 86.1g (1.0mol) of methyl acrylate and 102.2g (1mol) of n-octanol are added into a photosensitization reactor to react at the room temperature of 25 ℃;
(2) adding 1.0g (about 1mmol) of photosensitization catalyst bengal red and 0.5g (about 5mmol) of auxiliary agent quinuclidine, and irradiating by a 15w ultraviolet lamp at 25 ℃ for reaction;
(3) after the reaction is finished, 125.1g of peach aldehyde is separated by rectification, and the yield is 80.1%.
The results of the preparation of the other different substrates and catalysts are shown in table 1:
table 1, list of different reaction substrates, temperature reactions:
note: the dosages of the materials are calculated according to molar ratio; the amount of the photosensitizer used refers to the amount of the photosensitizing catalyst used as a percentage of the molar amount of the acrylic acid or the propionic acid ester.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (10)
1. A method for preparing gamma lactone by photosensitization catalysis is characterized in that: taking acrylic acid or acrylic ester and n-alkanol as raw materials, reacting under the participation of a photosensitization catalyst and an auxiliary agent and under the irradiation of ultraviolet light to generate the propiolactone, and rectifying after the reaction is finished to obtain the pure propiolactone, wherein the reaction formula is formula (1);
the photosensitization catalyst is 5,10,15, 20-tetraphenylporphyrin, 5,10,15, 20-tetraphenylmanganoporphyrin, 5,10,15, 20-tetraphenylzinc porphyrin, bengal red, tris (2,2 '-bipyridyl) ruthenium chloride, tris (2,2' -bipyridyl) ruthenium bis (hexafluorophosphate) salt or rose bengal B, and the auxiliary agent is quinuclidine; wherein R substituents are independently selected from H, CH3Or C2H5Any one of them; in the reaction formula, n is independently selected from any one of 2, 3, 4, 5, 6, 7 or 8.
2. The method of claim 1, wherein: the photosensitization catalyst is tris (2,2' -bipyridyl) ruthenium chloride.
3. The method of claim 1, wherein: the molar ratio of the acrylic acid or the acrylic ester to the normal alkanol is 1:1 to 10.
4. The method of claim 3, wherein: the molar ratio of the acrylic acid or the acrylic ester to the normal alkanol is 1: 1.
5. The method of claim 1, wherein: the dosage of the photosensitization catalyst is 0.1-10% of the molar weight of acrylic acid or acrylic ester.
6. The method of claim 5, wherein: the amount of the photosensitization catalyst is 0.1% of the molar amount of acrylic acid or acrylic ester.
7. The method of claim 1, wherein: the molar ratio of the photosensitization catalyst to the auxiliary agent quinuclidine is 1: 0.1-10.
8. The method of claim 7, wherein: the molar ratio of the photosensitization catalyst to the auxiliary agent quinuclidine is 1: 1.
9. The method of claim 1, wherein: the reaction temperature is 0-60 ℃.
10. The method of claim 9, wherein: the temperature of the reaction was 25 ℃.
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| CN201710291103.1A CN108794432B (en) | 2017-04-28 | 2017-04-28 | Method for preparing gamma lactone by photosensitization catalysis |
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| CN108794432B true CN108794432B (en) | 2020-04-21 |
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| CN116102527B (en) * | 2023-01-09 | 2023-12-19 | 万华化学集团股份有限公司 | Preparation method of peach aldehyde |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0338600A1 (en) * | 1988-01-28 | 1989-10-25 | Merck & Co. Inc. | Process for the preparation of prolinolamide derivatives |
| EP0548774A1 (en) * | 1991-12-25 | 1993-06-30 | Sumitomo Chemical Company, Limited | Process for producing a lactone or an ester |
| CN102391215A (en) * | 2011-10-25 | 2012-03-28 | 靖江泰达香料化工有限公司 | Synthesis method of chiral gamma-dodecalactone |
| CN103030614A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Extracting method of synthetic peach aldehyde |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002069064A (en) * | 2000-08-24 | 2002-03-08 | New Japan Chem Co Ltd | METHOD FOR PRODUCING gamma-BUTYROLACTONE |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0338600A1 (en) * | 1988-01-28 | 1989-10-25 | Merck & Co. Inc. | Process for the preparation of prolinolamide derivatives |
| EP0548774A1 (en) * | 1991-12-25 | 1993-06-30 | Sumitomo Chemical Company, Limited | Process for producing a lactone or an ester |
| CN103030614A (en) * | 2011-09-29 | 2013-04-10 | 南昌洋浦天然香料香精有限公司 | Extracting method of synthetic peach aldehyde |
| CN102391215A (en) * | 2011-10-25 | 2012-03-28 | 靖江泰达香料化工有限公司 | Synthesis method of chiral gamma-dodecalactone |
Non-Patent Citations (2)
| Title |
|---|
| O–H hydrogen bonding promotes H-atom transfer from α C-H bonds for C-alkylation of alcohols;Jenna L. Jeffrey et al.;《Science》;20150827;第349卷(第6255期);第1532-1536页 * |
| γ-十一内酯的合成研究;周作良等;《江西科学》;20150831;第33卷(第4期);第475-479页 * |
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