CN108794432A - A kind of method that photosensitizer catalysis prepares the third butyrolactone - Google Patents
A kind of method that photosensitizer catalysis prepares the third butyrolactone Download PDFInfo
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- CN108794432A CN108794432A CN201710291103.1A CN201710291103A CN108794432A CN 108794432 A CN108794432 A CN 108794432A CN 201710291103 A CN201710291103 A CN 201710291103A CN 108794432 A CN108794432 A CN 108794432A
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- photosensitizer
- acid
- butyrolactone
- method described
- catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—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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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to fragrance technical fields, and in particular to a kind of method that photosensitizer catalysis prepares the third butyrolactone.The present invention is using acrylic acid or acrylate and N-alkanes alcohol as raw material, using photosensitizer catalyst and auxiliary agent as catalyst, is reacted under ultraviolet light and generates the third butyrolactone, rectifying after reaction obtains the third butyrolactone sterling.Preparation method yield of the present invention is higher, is conducive to improve production capacity, reaches as high as 89.3%；For traditional handicraft, spent acid, waste water is avoided to generate；The addition of traditional handicraft peroxide radical initiator is avoided, opposite traditional handicraft is safely controllable.
Description
Technical field
The invention belongs to fragrance technical fields, and in particular to a kind of method that photosensitizer catalysis prepares the third butyrolactone.
Background technology
Third butyrolactone is the higher a kind of lactone series fragrance of essence and flavoring agent field value, since its threshold value is low, photo-thermal is steady
It is qualitative and fat-soluble good, in the industries extensive use such as food industry, daily use chemicals, health-care hospital.
The main synthesis technology of third butyrolactone is divided into two classes, and the first kind is olefin(e) acid sulfuric acid catalysis cyclization technique, representative work
Industry production technology is that undecenoic acid prepares peach aldehyde technique by sulfuric acid catalysis；Second class is N-alkanes alcohol and acrylic acid or acrylic acid
Methyl esters free radical addition technique (such as CN101402628A, CN102838569B), representative processes are acrylic acid or acrylic acid first
Ester prepares peach aldehyde and arbricolin with n-octyl alcohol and n-hexyl alcohol.Currently, the big production of industry mainly uses this according to raw material sources advantage
Two kinds of techniques.
The third usual yield of butyrolactone technique is not high, three-waste pollution is serious.First kind technique uses sulfuric acid, yield about 50-
60%.This technique generates a large amount of waste acid waters, and organic waste materials are higher.The second same yield of class technique only exists in 65-75%, great Liang You
Machine waste material needs to handle, and pollutes environment.It is 180 DEG C to react optimum temperature, reaction process N-alkanes alcohol/acrylic acid (methyl esters) about 6-
8, a large amount of N-alkanes alcohol recycle, and energy consumption is higher.Industry had developed some solid supported catalysts and prepares lactone in recent years
A kind of method, as HeFei University of Technology Zhou Lin provides γ-Al2O3The Pd-Ni Catalyzed by Pt/M Bimetallic Nano of load synthesizes γ-ten
The method of one lactone is prepared for γ-Al in this method using infusion process2O3The Pd-Ni bimetallic catalysts of load, the catalyst
In containing noble metal increase production cost to a certain extent.
So a kind of easy to operate, high income of exploitation, the technique of green high-efficient have important meaning to prepare the third butyrolactone
Justice.
Invention content
The purpose of the present invention is overcoming in the prior art the technical problem that product yield is not high, environmental pollution is big, one is provided
The method that the catalysis of kind of photosensitizer prepares the third butyrolactone, the present invention using acrylic acid or acrylate with N-alkanes alcohol as raw material,
Under photosensitizer catalysts conditions the third butyrolactone is prepared using illumination method.
The present invention is achieved through the following technical solutions above-mentioned purpose, and a kind of photosensitizer catalysis prepares the side of the third butyrolactone
Method, using acrylic acid or acrylate and N-alkanes alcohol as raw material, using photosensitizer catalyst and auxiliary agent as catalyst, in ultraviolet light
The lower reaction of irradiation generates the third butyrolactone, and rectifying after reaction obtains the third butyrolactone sterling；
Reaction equation is as shown in (1) formula：
Preferably, R substituent is independent in reaction equation is selected from H, CH3Or C2H5In any one；
Preferably, in reaction equation n it is independent in 2,3,4,5,6,7 or 8 any one；
Photosensitizer catalyst of the present invention is 5,10,15,20- tetraphenylporphyrins, 5,10,15,20- tetraphenyl manganese porphins
Quinoline, 5,10,15,20- tetraphenyls zinc protoporphyrin, rose-bengal, chlorination three (bipy 2,2' bipyridyl) ruthenium, three (2,2'- bipyridyls) rutheniums two
Any one in (hexafluorophosphoric acid) salt or rose red b, preferably chlorination three (2,2 '-bipyridyl) ruthenium；
Auxiliary agent of the present invention is quinuclidine, i.e. 1- azabicyclics [2.2.2] octane；
The method that photosensitizer catalysis of the present invention prepares the third butyrolactone, further technical solution is, described in preparation method
The molar ratio of propionic acid acid or propionic acid acid esters and N-alkanes alcohol is 1：(1~10), preferably 1:1；
The method that photosensitizer catalysis of the present invention prepares the third butyrolactone, further technical solution is, described in preparation method
Photosensitizer catalyst usage amount is acrylic acid or the 0.1%-10% of propionic acid acid esters mole, and optimal is 0.1%；
The method that photosensitizer catalysis of the present invention prepares the third butyrolactone, further technical solution is, described in preparation method
The molar ratio of photosensitizer catalyst and auxiliary agent quinuclidine is 1：(0.1-10), best proportion 1:1；
The method that photosensitizer catalysis of the present invention prepares the third butyrolactone, further technical solution is, in preparation method, reaction
Temperature is 0-60 DEG C, and peak optimization reaction temperature is 10-40 DEG C, further preferably 25 DEG C；
The present invention takes photosensitizer catalysis to prepare the third butyrolactone and provides optimal selection to substitute traditional handicraft, this technique is straight
Addition photosensitizer catalyst and auxiliary agent were connected, free radical addition cyclization is realized using illumination.
Compared with prior art, the invention has the advantages that：
1) preparation method yield of the present invention is higher, is conducive to improve production capacity, reaches as high as 89.3%；
2) present invention avoids spent acid, waste water from generating relative to traditional handicraft；
3) present invention avoids the addition of traditional handicraft peroxide radical initiator, opposite traditional handicraft safely controllable；
4) illumination reaction is milder with respect to conventional high temperature process condition, and energy consumption is relatively low.
Specific implementation mode
In order to make the objectives, technical solutions and advantages of the present invention clearer, With reference to embodiment, to this
Invention is further described.It should be understood that these descriptions are merely illustrative, and it is not intended to limit the scope of the present invention.
Embodiment 1
(1) in Photosensitive reaction device, acrylic acid 72.1g (1.0mol) and n-octyl alcohol 130.2g (1mol), heating is added
To 40 DEG C；
(2) photosensitizer catalyst 5,10,15,20- tetraphenylporphyrins 0.6g (1mmol) and auxiliary agent quinuclidine 0.1g is added
(~1mmol), 15w ultra violet lamps react at 40 DEG C；
(3) after completion of the reaction, (rectifying pressure 30Pa, 160 DEG C of kettle temperature, 121 degrees Celsius of tower top temperature, GC contains for rectifying separation
Amount >=98.5%) product peach aldehyde 151.7g, yield 82.3%.
Embodiment 2
(1) in Photosensitive reaction device, methyl acrylate 86.1g (1.0mol) and n-octyl alcohol 102.2g (1mol) is added,
25 DEG C of reactions of room temperature；
(2) photosensitizer catalyst rose-bengal 1.0g (~1mmol) and auxiliary agent quinuclidine 0.5g (~5mmol), 15w is added
Ultra violet lamp reacts at 25 DEG C；
(3) after completion of the reaction, rectifying separation product peach aldehyde 125.1g, yield 80.1%.
The preparation of other difference substrates and catalyst the results are shown in Table 1：
Table 1, differential responses substrate, thermotonus list:
Note：The dosage of the above material is calculated according to molar ratio；Photosensitizer usage amount refers to that photosensitizer catalyst uses
Amount is acrylic acid or the percentage of propionic acid acid esters mole.
Although embodiments of the present invention are described in detail, it should be understood that, without departing from the present invention's
In the case of spirit and scope, can embodiments of the present invention be made with various changes, replacement and change.
Claims (10)
1. a kind of method that photosensitizer catalysis prepares the third butyrolactone, it is characterised in that：With acrylic acid or acrylate and positive structure
Alkanol is raw material, in the presence of photosensitizer catalyst and auxiliary agent, the third butyrolactone of reaction generation under ultraviolet light, and reaction knot
Rectifying obtains the third butyrolactone sterling after beam, and reaction equation is formula (1)；
The photosensitizer catalyst be 5,10,15,20- tetraphenylporphyrins, 5,10,15,20- tetraphenyls manganoporphyrin, 5,10,15,
20- tetraphenyls zinc protoporphyrin, rose-bengal, chlorination three (bipy 2,2' bipyridyl) ruthenium, three (2,2'- bipyridyls) rutheniums two (hexafluorophosphoric acid)
Salt or rose red b, the auxiliary agent are quinuclidine.
2. according to the method described in claim 1, it is characterized in that：The photosensitizer catalyst is the (2,2 '-connection pyrroles of chlorination three
Pyridine) ruthenium.
3. according to the method described in claim 1, it is characterized in that：Mole of the propionic acid acid or propionic acid acid esters and N-alkanes alcohol
Than being 1：1~10.
4. according to the method described in claim 3, it is characterized in that：Mole of the propionic acid acid or propionic acid acid esters and N-alkanes alcohol
Than being 1:1.
5. according to the method described in claim 1, it is characterized in that：The photosensitizer catalyst usage amount is acrylic acid or propionic acid
The 0.1%-10% of acid esters mole.
6. according to the method described in claim 5, it is characterized in that：The photosensitizer catalyst usage amount is acrylic acid or propionic acid
The 0.1% of acid esters mole.
7. according to the method described in claim 1, it is characterized in that：The molar ratio of the photosensitizer catalyst and auxiliary agent quinuclidine
It is 1：0.1-10.
8. according to the method described in claim 7, it is characterized in that：The molar ratio of the photosensitizer catalyst and auxiliary agent quinuclidine
It is 1:1.
9. according to the method described in claim 1, it is characterized in that：The temperature of reaction is 0-60 DEG C.
10. according to the method described in claim 9, it is characterized in that：The temperature of reaction is 25 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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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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| CN201710291103.1A CN108794432B (en) | 2017-04-28 | 2017-04-28 | Method for preparing gamma lactone by photosensitization catalysis |
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| CN108794432A true CN108794432A (en) | 2018-11-13 |
| CN108794432B CN108794432B (en) | 2020-04-21 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102527A (en) * | 2023-01-09 | 2023-05-12 | 万华化学集团股份有限公司 | Preparation method of peach aldehyde |
Citations (5)
| 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 |
| JP2002069064A (en) * | 2000-08-24 | 2002-03-08 | New Japan Chem Co Ltd | METHOD FOR PRODUCING gamma-BUTYROLACTONE |
| 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 |
-
2017
- 2017-04-28 CN CN201710291103.1A patent/CN108794432B/en active Active
Patent Citations (5)
| 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 |
| JP2002069064A (en) * | 2000-08-24 | 2002-03-08 | New Japan Chem Co Ltd | METHOD FOR PRODUCING gamma-BUTYROLACTONE |
| 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 |
|---|
| JENNA L. JEFFREY ET AL.: "O–H hydrogen bonding promotes H-atom transfer from α C-H bonds for C-alkylation of alcohols", 《SCIENCE》 * |
| 周作良等: "γ-十一内酯的合成研究", 《江西科学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116102527A (en) * | 2023-01-09 | 2023-05-12 | 万华化学集团股份有限公司 | Preparation method of peach aldehyde |
| 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 |
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| CN108794432B (en) | 2020-04-21 |
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