CN115872953B - Preparation method of peach aldehyde - Google Patents
Preparation method of peach aldehyde Download PDFInfo
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- CN115872953B CN115872953B CN202211562911.4A CN202211562911A CN115872953B CN 115872953 B CN115872953 B CN 115872953B CN 202211562911 A CN202211562911 A CN 202211562911A CN 115872953 B CN115872953 B CN 115872953B
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- methyl acrylate
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- PHXATPHONSXBIL-UHFFFAOYSA-N xi-gamma-Undecalactone Chemical compound CCCCCCCC1CCC(=O)O1 PHXATPHONSXBIL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 72
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 58
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 51
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 238000007348 radical reaction Methods 0.000 claims abstract description 6
- 150000003254 radicals Chemical class 0.000 claims abstract description 6
- 239000003377 acid catalyst Substances 0.000 claims abstract description 5
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 9
- -1 diethylpropylbenzene hydroperoxide Chemical compound 0.000 claims description 8
- QIWRFOJWQSSRJZ-UHFFFAOYSA-N tributyl(ethenyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C=C QIWRFOJWQSSRJZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- ZBBLRPRYYSJUCZ-GRHBHMESSA-L (z)-but-2-enedioate;dibutyltin(2+) Chemical compound [O-]C(=O)\C=C/C([O-])=O.CCCC[Sn+2]CCCC ZBBLRPRYYSJUCZ-GRHBHMESSA-L 0.000 claims description 4
- JJRDRFZYKKFYMO-UHFFFAOYSA-N 2-methyl-2-(2-methylbutan-2-ylperoxy)butane Chemical compound CCC(C)(C)OOC(C)(C)CC JJRDRFZYKKFYMO-UHFFFAOYSA-N 0.000 claims description 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- RFSCGDQQLKVJEJ-UHFFFAOYSA-N 2-methylbutan-2-yl benzenecarboperoxoate Chemical compound CCC(C)(C)OOC(=O)C1=CC=CC=C1 RFSCGDQQLKVJEJ-UHFFFAOYSA-N 0.000 claims description 2
- XYFRHHAYSXIKGH-UHFFFAOYSA-N 3-(5-methoxy-2-methoxycarbonyl-1h-indol-3-yl)prop-2-enoic acid Chemical compound C1=C(OC)C=C2C(C=CC(O)=O)=C(C(=O)OC)NC2=C1 XYFRHHAYSXIKGH-UHFFFAOYSA-N 0.000 claims description 2
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 2
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 claims description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 claims description 2
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 6
- 239000004327 boric acid Substances 0.000 description 6
- 230000007547 defect Effects 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- XEXIVNNTJNBUGV-UHFFFAOYSA-N 4-hydroxy-undecanoic acid Chemical compound CCCCCCCC(O)CCC(O)=O XEXIVNNTJNBUGV-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 244000144730 Amygdalus persica Species 0.000 description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 150000001261 hydroxy acids Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- SWAXTRYEYUTSAP-UHFFFAOYSA-N tert-butyl ethaneperoxoate Chemical compound CC(=O)OOC(C)(C)C SWAXTRYEYUTSAP-UHFFFAOYSA-N 0.000 description 2
- 229960002703 undecylenic acid Drugs 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QEQBMZQFDDDTPN-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy benzenecarboperoxoate Chemical compound CC(C)(C)OOOC(=O)C1=CC=CC=C1 QEQBMZQFDDDTPN-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- FRPZMMHWLSIFAZ-UHFFFAOYSA-N 10-undecenoic acid Chemical compound OC(=O)CCCCCCCCC=C FRPZMMHWLSIFAZ-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000009844 Cucumis melo var conomon Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 244000242564 Osmanthus fragrans Species 0.000 description 1
- 235000019083 Osmanthus fragrans Nutrition 0.000 description 1
- FJJCIZWZNKZHII-UHFFFAOYSA-N [4,6-bis(cyanoamino)-1,3,5-triazin-2-yl]cyanamide Chemical compound N#CNC1=NC(NC#N)=NC(NC#N)=N1 FJJCIZWZNKZHII-UHFFFAOYSA-N 0.000 description 1
- CPLPNZFTIJOEIN-UHFFFAOYSA-I [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O Chemical compound [V+5].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O CPLPNZFTIJOEIN-UHFFFAOYSA-I 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- KHAVLLBUVKBTBG-UHFFFAOYSA-N caproleic acid Natural products OC(=O)CCCCCCCC=C KHAVLLBUVKBTBG-UHFFFAOYSA-N 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- PHXATPHONSXBIL-JTQLQIEISA-N gamma-Undecalactone Natural products CCCCCCC[C@H]1CCC(=O)O1 PHXATPHONSXBIL-JTQLQIEISA-N 0.000 description 1
- 125000000457 gamma-lactone group Chemical group 0.000 description 1
- 229940020436 gamma-undecalactone Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000007273 lactonization reaction Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of peach aldehyde. The method comprises two steps of reaction, 1) taking n-octanol and methyl acrylate as raw materials, and carrying out free radical reaction under the action of peroxide and an auxiliary agent to generate an acid alcohol intermediate; 2) Taking an acid alcohol intermediate as a raw material, and carrying out esterification reaction under the action of an acid catalyst to prepare the peach aldehyde. The invention solves the problem that the intermittent process is adopted in the conventional synthesis of peach aldehyde, improves the continuity and stability of production operation, greatly reduces the generation of impurities, improves the yield of peach aldehyde, and solves the problems of high separation difficulty, more waste liquid and low yield of peach aldehyde.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of peach aldehyde.
Background
Peach aldehyde is commonly called as propionoundecalactone, also called as tetradecal and gamma-undecalactone, is colorless to pale yellow liquid, has the taste of peach, fruit and cream, is an essence additive for preparing food and beverage such as peach, cherry, sweet osmanthus, melon and the like, and is widely applied to daily chemical essence and edible essence.
At present, the synthesis of peach aldehyde mainly adopts the following methods:
(1) Under the action of sulfuric acid and hydrochloric acid catalyst, hydroxy acid, hydroxy ester and hydroxy acid derivative are synthesized directly into gamma-lactone in molecule, and the disadvantage is that raw materials 4-hydroxy undecanoic acid, 4-hydroxy undecanoic acid ester and 4-hydroxy undecanoic acid derivative are difficult to obtain and are not suitable for industrial production.
(2) Under the action of sulfuric acid catalyst, beta, gamma-undecylenic acid is synthesized by lactonization, which has the defects of complex preparation route of undecylenic acid, high synthesis cost, large amount of waste liquid generated in the production process and high three-waste treatment cost.
(3) The cerium acetate and the vanadium acetate are used as oxidizing agents and are prepared by synthesizing alpha-nonene and acetic acid, and the defects are that a large amount of heavy metal wastewater is generated by reaction, the heavy metal wastewater is difficult to treat, and the cost is high, so that the method is not suitable for industrial mass production.
(4) Under the action of boric acid catalyst, acrylic acid or methyl acrylate and n-octanol are adopted as raw materials, and free radical reaction is carried out under the action of peroxide initiator to prepare peach aldehyde, thus being a synthesis route for large-scale industrial application. The intermittent one-pot production process adopted in the industrial production has the defects of poor intermittent reaction continuity, long reaction time, low production efficiency and low separation yield, and the reaction liquid contains a large amount of low-boiling-point and high-boiling-point impurities, so that the fragrance of the product is not pure, and the fragrance of the peach aldehyde needs to be improved through complex fragrance aftertreatment.
Patent CN112275234A discloses a peach aldehyde production system and a production method, n-octanol, acrylic acid and di-tert-butyl peroxide are uniformly mixed in a raw material tank according to a proportion, n-octanol and boric acid serving as a catalyst are added in a reaction kettle in advance, raw materials are added dropwise after the temperature is raised to 140-180 ℃, the dropwise adding time is 6-12 h, the reaction is continued for 1-2 h after the dropwise adding is finished, the product yield is 85%, and a protective gas is required to be introduced in the dropwise adding process to reduce the dropwise adding temperature of the raw materials so as to reduce the occurrence of side reaction.
Patent CN103030614A discloses an extraction method for synthesizing peach aldehyde, which comprises the steps of firstly mixing octanol, acrylic acid and peroxide, adding octanol and a catalyst into a reaction kettle, heating to 140-190 ℃, dripping the mixture of octanol, acrylic acid and peroxide into the reaction kettle within 4-10 hours, stopping the reaction after no byproduct water is generated, rectifying reaction liquid to obtain a pure peach aldehyde product, wherein the peach aldehyde yield is 73.5%, and the pure peach aldehyde product also needs to be subjected to special aroma treatment for 1-6 hours.
Patent CN214183032U discloses a peach aldehyde production system, firstly, raw materials of n-octanol, acrylic acid and di-tert-butyl peroxide are uniformly mixed in a raw material tank according to a feeding proportion, a proper amount of n-octanol and boric acid are added into a reaction kettle, a mixture of n-octanol, acrylic acid and di-tert-butyl peroxide is dropwise added after the temperature is raised to 160-180 ℃, the dropwise adding time is 8-10 h, the reaction is continued for 1h after the dropwise adding is finished, the reaction liquid is rectified to obtain peach aldehyde with the GC purity of more than 99.5%, the peach aldehyde yield is 84-86%, and the method has the defects of long reaction time and complex intermittent operation and cannot meet the requirement of large-scale production.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides a preparation method of peach aldehyde, which overcomes the defects of the prior art for synthesizing peach aldehyde, has the advantages of short reaction time, high product yield, low three wastes and energy consumption, low production cost and strong continuous operability, and is very suitable for large-scale industrialized amplification.
In order to achieve the above purpose and the above reaction effect, the present invention adopts the following technical scheme:
the invention provides a preparation method of peach aldehyde, which comprises the following steps:
1) N-octanol and methyl acrylate are used as raw materials, and free radical reaction is carried out under the action of peroxide and auxiliary agent to generate an acid alcohol intermediate;
2) Taking an acid alcohol intermediate as a raw material, and carrying out esterification reaction under the action of an acid catalyst to prepare the peach aldehyde.
In the present invention, the peroxide in step 1) is selected from one or more of di-t-butyl peroxide, dibenzoyl peroxide, di-t-amyl peroxide, t-butyl peroxyacetate, t-butyl peroxybenzoate, t-amyl peroxybenzoate, diisopropyl peroxydicarbonate, diethylpropylbenzene hydroperoxide, isopropylbenzene hydroperoxide, preferably one or more of di-t-butyl peroxide, di-t-amyl peroxide, t-butyl peroxyacetate.
In the present invention, the auxiliary agent in step 1) is selected from one or more of tri-n-butyl (vinyl) tin, dibutyl tin diacetate and dibutyl tin maleate, preferably tri-n-butyl (vinyl) tin.
In the present invention, the molar ratio of n-octanol to methyl acrylate in step 1) is 5-10:1, preferably 6-8:1.
In the present invention, the molar ratio of methyl acrylate to peroxide in step 1) is 10 to 20:1, preferably 14 to 16:1.
In the present invention, the auxiliary agent in step 1) is used in an amount of 0.01 to 0.5% by mass, preferably 0.05 to 0.2% by mass, based on the mass of the peroxide.
In the present invention, the temperature of the reaction in step 1) is 150 to 210℃and preferably 170 to 190 ℃.
In the present invention, the reaction time in step 1) is 15 to 120 seconds, preferably 30 to 60 seconds.
Preferably, in the present invention, the radical reaction of step 1) is carried out in a tubular reactor followed by a cooling heat exchanger and a storage tank, the reaction solution being rapidly cooled, wherein the preferred cooling temperature is from 0 to 20 ℃, preferably from 5 to 10 ℃.
In the invention, the free radical reaction in the step 1) has a conversion rate of more than 99.9 percent and a selectivity of more than 98 percent of the acid-alcohol intermediate.
In the invention, the esterification reaction in the step 2) is carried out under the condition of an acidic catalyst, wherein the acidic catalyst is one or more of sulfuric acid, nitric acid, hydrochloric acid, p-toluenesulfonic acid and boric acid, and preferably one or more of sulfuric acid, p-toluenesulfonic acid and hydrochloric acid.
Preferably, in step 2), the amount of the acid catalyst is 0.01 to 1%, preferably 0.05 to 0.2% by mass of the acid alcohol intermediate.
In the present invention, the temperature of the reaction in step 2) is 110 to 180℃and preferably 120 to 160 ℃.
In the present invention, in step 2), the reaction residence time is 10 to 60 minutes, preferably 15 to 30 minutes.
In the invention, the esterification reaction in the step 2) has the conversion rate of the acid-alcohol intermediate of more than 99.5 percent and the selectivity of peach aldehyde of more than 99 percent.
As a preferable scheme, the first step is tubular reaction, and the second step is scraper reaction rectification. The first step is to introduce a mixture containing n-octanol, methyl acrylate, peroxide and an auxiliary agent into a tubular reactor for reaction to obtain an acid-alcohol intermediate mixture, and the second step is to introduce the acid-alcohol intermediate mixture and an acid catalyst into a scraper reaction rectifying tower for mixing, and remove methanol to generate peach aldehyde.
One or more of adjuvants such as tri-n-butyl (vinyl) tin, dibutyl tin diacetate, dibutyl tin maleate and the like are introduced in the first step of reaction process, so that the stability of peroxide radicals and n-octanol radicals can be improved, the side reaction of the peroxide radicals and the n-octanol radicals in the reaction liquid is reduced, the free radical addition reaction of the n-octanol radicals and methyl acrylate is promoted, the side reaction such as methyl acrylate polymerization is reduced, and the selectivity and the conversion rate of methyl acrylate are improved.
Detailed Description
The reaction results were detected by gas chromatograph under the following specific analysis conditions: the chromatographic instrument is Agilent 7890A, the model of chromatographic column is HP-5, the inner diameter is 320 μm, the length is 30m, and the highest temperature is 325 ℃. Heating program: first, the temperature is kept at 60℃for 1 minute, the temperature is raised to 200℃at 15℃for 2 minutes, the temperature is raised to 300℃at 20℃for 15 minutes, and the total running time is 32 minutes.
Example 1
200g of n-octanol, 18.9g of methyl acrylate, 2.13g of di-tert-butyl peroxide and 0.0021g of tri-n-butyl (vinyl) tin are uniformly mixed, reacted in a tubular reactor at 180 ℃ for 40 seconds, and then cooled to 10 ℃ by a cooler after the reaction, wherein the conversion rate of the methyl acrylate is 99.9%, and the selectivity of an acid alcohol intermediate is 98.5%.
Adding 0.0467g of sulfuric acid into the reaction liquid, continuously introducing into a scraper reaction rectifying tower, reacting for 20min at 150 ℃, extracting methanol generated by the reaction at the top of the tower, and obtaining a mixed liquid containing peach aldehyde at the bottom of the tower, wherein the conversion rate of an acid-alcohol intermediate is 99.7%, and the selectivity is 99.4%.
Example 2
210g of n-octanol, 14g of methyl acrylate, 2.8g of di-tert-amyl peroxide and 0.01g of dibutyltin diacetate are uniformly mixed, reacted in a tubular reactor at 155 ℃ for 110 seconds, and then cooled to 10 ℃ by a cooler after the reaction is finished, wherein the conversion rate of the methyl acrylate is 99.95%, and the selectivity of an acid alcohol intermediate is 98.9%.
Adding 0.0052g of hydrochloric acid into the reaction liquid, continuously introducing into a scraper reaction rectifying tower, reacting for 58min at 115 ℃, extracting methanol generated by the reaction at the top of the tower, and obtaining a mixed liquid containing peach aldehyde at the bottom of the tower, wherein the conversion rate of an acid-alcohol intermediate is 99.6%, and the selectivity is 99.3%.
Example 3
210g of n-octanol, 25g of methyl acrylate, 2.4g of tert-butyl peroxyacetate and 0.0135g of tri-n-butyl (vinyl) tin are uniformly mixed, reacted for 30s in a tubular reactor at 190 ℃, and then cooled to 10 ℃ by a cooler after the reaction, wherein the conversion rate of the methyl acrylate is 99.97%, and the selectivity of an acid alcohol intermediate is 98.7%.
0.4956g of boric acid is added into the reaction liquid, the mixture is continuously introduced into a scraper reaction rectifying tower, the reaction is carried out for 10min at 178 ℃, methanol generated by the reaction is extracted from the top of the tower, the mixed liquid containing peach aldehyde is obtained from the tower kettle, and the conversion rate of the acid-alcohol intermediate is 99.8% and the selectivity is 99.1%.
Example 4
200g of n-octanol, 16.5g of methyl acrylate, 2.6g of tert-butyl peroxybenzoate and 0.004g of dibutyl tin maleate are uniformly mixed, reacted in a tubular reactor at 170 ℃ for 60 seconds, and then cooled to 10 ℃ by a cooler after the reaction, wherein the conversion rate of the methyl acrylate is 99.96%, and the selectivity of an acid alcohol intermediate is 98.8%.
0.082g of p-toluenesulfonic acid is added into the reaction liquid, the mixture is continuously introduced into a scraper reaction rectifying tower to react for 30min at 160 ℃, methanol generated by the reaction is extracted from the tower top, and the mixed liquid containing peach aldehyde is obtained from the tower bottom, wherein the conversion rate of acid-alcohol intermediate is 99.7%, and the selectivity is 99.35%.
Example 5
230g of n-octanol, 25g of methyl acrylate, 2.2g of di-tert-butyl peroxide and 0.0004g of tri-n-butyl (vinyl) tin are uniformly mixed, reacted for 16s in a tubular reactor at 205 ℃, and then cooled to 10 ℃ by a cooler after the reaction, wherein the conversion rate of the methyl acrylate is 99.98%, and the selectivity of an acid alcohol intermediate is 98.3%.
Adding 0.092g of sulfuric acid into the reaction liquid, continuously introducing into a scraper reaction rectifying tower, reacting for 15min at 130 ℃, extracting methanol generated by the reaction at the top of the tower, and obtaining a mixed liquid containing peach aldehyde at the bottom of the tower, wherein the conversion rate of an acid-alcohol intermediate is 99.7%, and the selectivity is 99.20%.
Comparative example 1
200g of n-octanol, 18.9g of methyl acrylate and 2.13g of di-tert-butyl peroxide are uniformly mixed, reacted in a tubular reactor at 180 ℃ for 40 seconds, and then cooled to 10 ℃ by a cooler after the reaction is finished, wherein the conversion rate of methyl acrylate is 88%, and the selectivity of an acid alcohol intermediate is 72%.
Adding 0.0267g sulfuric acid into the reaction liquid, continuously introducing into a scraper reaction rectifying tower, reacting for 20min at 150 ℃, extracting methanol generated by the reaction at the top of the tower, and obtaining a mixed liquid containing peach aldehyde at the bottom of the tower, wherein the conversion rate of an acid-alcohol intermediate is 99.5%, and the selectivity is 99%.
Comparative example 2
Firstly, 18g of n-octanol, 18g of methyl acrylate and 2.1g of di-tert-butyl peroxide are uniformly mixed, 182g of n-octanol and 0.22 boric acid are added into a reaction kettle, the mixed liquid of n-octanol, methyl acrylate and di-tert-butyl peroxide is dripped into the reaction kettle after the temperature of the reaction kettle is raised to 180 ℃, the dripping time is 6 hours, the reaction is continued for 1.5 hours after the dripping is finished, the reaction is cooled after the reaction is finished, the conversion rate of methyl acrylate is 99.8%, and the selectivity is 82%.
Claims (15)
1. A preparation method of peach aldehyde comprises the following steps:
1) N-octanol and methyl acrylate are used as raw materials, and free radical reaction is carried out under the action of peroxide and auxiliary agent to generate an acid alcohol intermediate;
2) Taking an acid alcohol intermediate as a raw material, and carrying out esterification reaction under the action of an acid catalyst to prepare peach aldehyde;
step 1) the peroxide is selected from one or more of di-tert-butyl peroxide, dibenzoyl peroxide, di-tert-amyl peroxide, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, tert-amyl peroxybenzoate, diisopropyl peroxydicarbonate, diethylpropylbenzene hydroperoxide and isopropylbenzene hydroperoxide;
the auxiliary agent in the step 1) is selected from one or more of tri-n-butyl (vinyl) tin, dibutyl tin diacetate and dibutyl tin maleate.
2. The method according to claim 1, wherein the molar ratio of n-octanol to methyl acrylate in step 1) is 5-10:1.
3. The method according to claim 1, wherein the molar ratio of n-octanol to methyl acrylate in step 1) is 6-8:1.
4. The method of claim 1, wherein the molar ratio of methyl acrylate to peroxide in step 1) is from 10 to 20:1.
5. The method of claim 1, wherein the molar ratio of methyl acrylate to peroxide in step 1) is 14-16:1.
6. The method according to claim 1, wherein the auxiliary agent in step 1) is used in an amount of 0.01 to 0.5% by mass of the peroxide.
7. The method according to claim 1, wherein the auxiliary agent in step 1) is used in an amount of 0.05 to 0.2% by mass of the peroxide.
8. The method according to claim 1, wherein the temperature of the reaction of step 1) is 150 to 210 ℃; the reaction time is 15-120 s.
9. The method according to claim 1, wherein the temperature of the reaction of step 1) is 170-190 ℃; the reaction time is 30-60 s.
10. The method according to claim 1, wherein after the reaction in step 1), the reaction solution is cooled at 0 to 20 ℃.
11. The method according to claim 1, wherein after the reaction in step 1), the reaction solution is cooled at 5 to 10 ℃.
12. The method according to claim 1, wherein in the step 2), the amount of the acidic catalyst is 0.01 to 1% by mass of the acid alcohol intermediate.
13. The method according to claim 1, wherein in the step 2), the amount of the acidic catalyst is 0.05 to 0.2% by mass of the acid alcohol intermediate.
14. The method according to claim 1, wherein the temperature of the reaction of step 2) is 110-180 ℃; the reaction residence time is 10-60 min.
15. The method according to claim 1, wherein the temperature of the reaction of step 2) is 120-160 ℃; the reaction residence time is 15-30 min.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001011063A (en) * | 1999-04-30 | 2001-01-16 | Soda Aromatic Co Ltd | Production of optically active gamma-lactone |
| 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 |
| CN107735438A (en) * | 2015-05-11 | 2018-02-23 | Sika技术股份公司 | Catalyst containing guanidine radicals |
| CN115322833A (en) * | 2016-12-21 | 2022-11-11 | 西姆莱斯股份公司 | Perfume mixture |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001011063A (en) * | 1999-04-30 | 2001-01-16 | Soda Aromatic Co Ltd | Production of optically active gamma-lactone |
| 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 |
| CN107735438A (en) * | 2015-05-11 | 2018-02-23 | Sika技术股份公司 | Catalyst containing guanidine radicals |
| CN115322833A (en) * | 2016-12-21 | 2022-11-11 | 西姆莱斯股份公司 | Perfume mixture |
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