CN115872953A - Preparation method of peach aldehyde - Google Patents
Preparation method of peach aldehyde Download PDFInfo
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- CN115872953A CN115872953A CN202211562911.4A CN202211562911A CN115872953A CN 115872953 A CN115872953 A CN 115872953A CN 202211562911 A CN202211562911 A CN 202211562911A CN 115872953 A CN115872953 A CN 115872953A
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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 63
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims abstract description 54
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims abstract description 54
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 19
- 150000002978 peroxides Chemical class 0.000 claims abstract description 15
- 150000003254 radicals Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000007348 radical reaction Methods 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 5
- 239000003377 acid catalyst Substances 0.000 claims abstract description 3
- 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 10
- QIWRFOJWQSSRJZ-UHFFFAOYSA-N tributyl(ethenyl)stannane Chemical compound CCCC[Sn](CCCC)(CCCC)C=C QIWRFOJWQSSRJZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 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
- 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 4
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 4
- -1 diethylpropylbenzene hydroperoxide Chemical compound 0.000 claims description 4
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 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
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 239000007788 liquid Substances 0.000 abstract description 6
- 230000002194 synthesizing effect Effects 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000012535 impurity Substances 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
- 239000000203 mixture Substances 0.000 description 13
- 239000012295 chemical reaction liquid Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 230000007547 defect Effects 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
- 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
- 239000011259 mixed solution Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 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
- 238000001816 cooling Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 244000144730 Amygdalus persica Species 0.000 description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010438 heat treatment 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
- 230000001681 protective effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UHUFTBALEZWWIH-UHFFFAOYSA-N tetradecanal Chemical compound CCCCCCCCCCCCCC=O UHUFTBALEZWWIH-UHFFFAOYSA-N 0.000 description 2
- 229960002703 undecylenic acid Drugs 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 229910052684 Cerium Inorganic materials 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
- 230000000996 additive effect Effects 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
- 230000015572 biosynthetic process Effects 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
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 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
- 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
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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 reactions, 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 obtain peach aldehyde. The method solves the problem of adopting an intermittent process for conventionally synthesizing peach aldehyde, improves the continuity and stability of production operation, greatly reduces the generation of impurities, improves the peach aldehyde yield, and solves the problems of high difficulty in separating peach aldehyde, more waste liquid and low yield.
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 propyl undecalactone, also called as tetradecanal and gamma undecalactone, is colorless to light yellow liquid, has the taste of peach, fruit and cream, is an essence additive for preparing foods and beverages such as peach, cherry, sweet osmanthus, melon and the like, and is widely applied to daily chemical essence and edible essence.
At present, the following method is mainly adopted for synthesizing peach aldehyde:
(1) Under the action of sulfuric acid and hydrochloric acid catalysts, hydroxy acid, hydroxy ester and hydroxy acid derivatives are directly synthesized into gamma-lactone in molecules, and the defects that the 4-hydroxyundecanoic acid, 4-hydroxyundecanoate and 4-hydroxyundecanoate derivatives are difficult to obtain and are not suitable for industrial production.
(2) Beta, gamma-undecylenic acid is synthesized by lactonization under the action of a sulfuric acid catalyst, and has the defects of complex preparation route of the undecylenic acid, high synthesis cost, large amount of waste liquid generated in the production process and high treatment cost of three wastes.
(3) Acetate of cerium and vanadium is taken as an oxidant and is synthesized by alpha-nonene and acetic acid, and the defects are that a large amount of heavy metal wastewater is generated in the reaction, the heavy metal wastewater is difficult to treat, the cost is high, and the method is not suitable for industrial large-scale production.
(4) Under the action of boric acid catalyst, acrylic acid or methyl acrylate and n-octanol are used as raw materials, and free radical reaction is carried out under the action of peroxide initiator to prepare peach aldehyde, so that the method is a synthetic route for large-scale industrial application. The intermittent one-pot production process is adopted in industrial production, and has the defects of poor continuous operability of intermittent reaction, long reaction time, low production efficiency, low separation yield, and impure product aroma caused by a large amount of low-boiling point and high-boiling point impurities contained in reaction liquid, and the aroma of peach aldehyde is improved by complex aroma post-treatment.
Patent CN112275234A discloses a peach aldehyde production system and a production method, wherein n-octanol, acrylic acid and di-tert-butyl peroxide are uniformly mixed in a raw material tank according to a proportion, n-octanol and catalyst boric acid are added in a reaction kettle in advance, the temperature is increased to 140-180 ℃, then raw materials are dripped, the dripping time is 6-12 h, the reaction is continued for 1-2 h after the dripping is finished, the product yield is 85%, protective gas is required to be introduced in the dripping process to reduce the dripping temperature of the raw materials to reduce the occurrence of side reaction, and the method has the defects of long reaction time, intermittent operation and additional protective gas addition, so that the production efficiency is low and the production cost is high.
Patent CN103030614A discloses an extraction method for synthesizing peach aldehyde, which comprises mixing octanol, acrylic acid and peroxide, adding octanol and a catalyst into a reaction kettle, heating to 140-190 ℃, dropwise adding the mixture of octanol, acrylic acid and peroxide into the reaction kettle within 4-10 h, stopping reaction until no byproduct water is produced, rectifying the reaction liquid to obtain a pure peach aldehyde product with a peach aldehyde yield of 73.5%, and subjecting the pure peach aldehyde product to special aroma treatment for 1-6 h.
Patent CN214183032U discloses a peach aldehyde production system, which comprises the steps of firstly, uniformly mixing raw materials of n-octanol, acrylic acid and di-tert-butyl peroxide in a raw material tank according to a feeding proportion, adding a proper amount of n-octanol and boric acid into a reaction kettle, heating to 160-180 ℃, dropwise adding a mixture of the n-octanol, the acrylic acid and the di-tert-butyl peroxide, wherein the dropwise adding time is 8-10 h, continuing to react for 1h after the dropwise adding is finished, rectifying reaction liquid to obtain peach aldehyde with the GC purity of more than 99.5%, and the peach aldehyde yield is 84-86%.
Disclosure of Invention
In order to make up for the defects in the prior art, the invention aims to provide a preparation method of peach aldehyde, which overcomes the technical defects of the prior method 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 industrial amplification.
In order to achieve the purpose and achieve the reaction effect, the invention adopts the following technical scheme:
the invention provides a preparation method of peach aldehyde, which comprises the following steps:
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 peach aldehyde.
In the invention, the peroxide in step 1) 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, and preferably one or more of di-tert-butyl peroxide, di-tert-amyl peroxide and tert-butyl peroxyacetate.
In the invention, the auxiliary agent in the step 1) is one or more selected from tri-n-butyl (vinyl) tin, dibutyltin diacetate and dibutyltin maleate, and the tri-n-butyl (vinyl) tin is preferred.
In the present invention, the molar ratio of n-octanol to methyl acrylate in step 1) is 5 to 10, preferably 6 to 8.
In the present invention, the molar ratio of the methyl acrylate to the peroxide in step 1) is 10 to 20, preferably 14 to 16.
In the invention, the amount of the auxiliary agent in the step 1) is 0.01-0.5%, preferably 0.05-0.2% of the mass of the peroxide.
In the present invention, the reaction temperature in step 1) is 150 to 210 ℃, 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 invention, the free radical reaction in the step 1) is carried out in a tubular reactor, the tubular reactor is followed by a cooling heat exchanger and a storage tank, and the reaction liquid is rapidly cooled, wherein the preferred cooling temperature is 0-20 ℃, preferably 5-10 ℃.
In the invention, the free radical reaction in the step 1) has a conversion rate of over 99.9 percent and acid-alcohol intermediate selectivity of over 98 percent.
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 acidic catalyst is 0.01 to 1%, preferably 0.05 to 0.2% of the mass of the acid alcohol intermediate.
In the invention, the reaction temperature in the step 2) is 110-180 ℃, preferably 120-160 ℃.
In the invention, in the step 2), the reaction residence time is 10-60 min, preferably 15-30 min.
In the invention, the esterification reaction in the step 2) has the conversion rate of an acid-alcohol intermediate of more than 99.5 percent and the selectivity of peach aldehyde of more than 99 percent.
As a preferred scheme, the first step is a tubular reaction, and the second step is a scraper reaction rectification. Firstly, introducing 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, secondly, mixing the acid-alcohol intermediate mixture with an acidic catalyst, introducing the mixture into a scraper reaction rectifying tower, and removing methanol to generate peach aldehyde.
In the first-step reaction process, one or more of additives of tri-n-butyl (vinyl) tin, dibutyltin diacetate, dibutyltin maleate and the like are introduced, so that the stability of peroxide free radicals and n-octanol free radicals can be improved, the side reaction of the peroxide free radicals and the n-octanol free radicals in reaction liquid is reduced, the free radical addition reaction of the n-octanol free radicals and methyl acrylate is promoted, the side reaction of methyl acrylate polymerization and the like is reduced, and the selectivity and the conversion rate of the methyl acrylate are improved.
Detailed Description
Detecting the reaction result by using a gas chromatograph, wherein the specific analysis conditions are as follows: the chromatograph apparatus was an Agilent 7890A, a column model HP-5, an internal diameter of 320 μm, a length of 30m, and a maximum temperature of 325 ℃. Temperature rising procedure: first, the temperature is maintained at 60 ℃ for 1 minute, the temperature is raised to 200 ℃ at 15 ℃/min for 2 minutes, the temperature is raised to 300 ℃ at 20 ℃/min 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 and react in a 180 ℃ tubular reactor for 40s, and after the reaction is finished, the mixture is introduced into a cooler to be cooled to 10 ℃, the conversion rate of the methyl acrylate is 99.9 percent, and the selectivity of an acid-alcohol intermediate is 98.5 percent.
Adding 0.0467g of sulfuric acid into the reaction solution, continuously introducing into a scraper reaction rectifying tower, reacting for 20min at 150 ℃, extracting methanol generated by the reaction at the tower top, and obtaining a mixed solution containing peach aldehyde at the tower bottom, wherein the conversion rate of an acid-alcohol intermediate is 99.7 percent, and the selectivity is 99.4 percent.
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 and react for 110s in a tubular reactor at the temperature of 155 ℃, and then the mixture is introduced into a cooler to be cooled to 10 ℃, the conversion rate of methyl acrylate is 99.95 percent, and the selectivity of an acid alcohol intermediate is 98.9 percent.
Adding 0.0052g of hydrochloric acid into the reaction solution, continuously introducing into a scraper reaction rectifying tower, reacting at 115 ℃ for 58min, extracting methanol generated by the reaction at the tower top, and obtaining a mixed solution containing peach aldehyde at the tower bottom, wherein the conversion rate of the 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 in a tubular reactor at 190 ℃ for 30s, and after the reaction is finished, the mixture is introduced into a cooler to be cooled to 10 ℃, the conversion rate of the methyl acrylate is 99.97 percent, and the selectivity of an acid-alcohol intermediate is 98.7 percent.
0.4956g of boric acid is added into the reaction liquid, the reaction liquid is continuously introduced into a scraper reaction rectifying tower to react for 10min at 178 ℃, methanol generated by the reaction is extracted from the tower top, a mixed liquid containing peach aldehyde is obtained from the tower bottom, the conversion rate of the acid-alcohol intermediate is 99.8 percent, and the selectivity is 99.1 percent.
Example 4
200g of n-octanol, 16.5g of methyl acrylate, 2.6g of tert-butyl peroxybenzoate and 0.004g of dibutyltin maleate are uniformly mixed and react for 60s in a tubular reactor at the temperature of 170 ℃, and after the reaction is finished, the mixture is introduced into a cooler to be cooled to 10 ℃, the conversion rate of the methyl acrylate is 99.96 percent, and the selectivity of an acid alcohol intermediate is 98.8 percent.
Adding 0.082g of p-toluenesulfonic acid into the reaction liquid, continuously introducing into a scraper reaction rectifying tower, reacting for 30min at 160 ℃, extracting methanol generated by the reaction at the tower top, and obtaining a mixed liquid containing peach aldehyde at the tower bottom, wherein the conversion rate of an 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 and react for 16s in a tubular reactor at 205 ℃, and after the reaction is finished, the mixture is introduced into a cooler to be cooled to 10 ℃, the conversion rate of the methyl acrylate is 99.98 percent, and the selectivity of an acid alcohol intermediate is 98.3 percent.
0.092g of sulfuric acid is added into the reaction liquid, the reaction liquid is continuously fed into a scraper reaction rectifying tower to react for 15min at 130 ℃, methanol generated by the reaction is extracted from the tower top, a mixed liquid containing peach aldehyde is obtained from the tower bottom, 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, the mixture reacts in a tubular reactor at 180 ℃ for 40s, and after the reaction is finished, the mixture is introduced into a cooler to be cooled to 10 ℃, the conversion rate of methyl acrylate is 88 percent, and the selectivity of an acid-alcohol intermediate is 72 percent.
Adding 0.0267g sulfuric acid into the reaction solution, continuously introducing into a scraper reaction rectifying tower, reacting at 150 deg.C for 20min, collecting methanol generated from the reaction at the tower top, and obtaining a mixed solution containing peach aldehyde at the tower bottom, wherein the conversion rate of the acid-alcohol intermediate is 99.5% and the selectivity is 99%.
Comparative example 2
Firstly, uniformly mixing 18g of n-octanol, 18g of methyl acrylate and 2.1g of di-tert-butyl peroxide, adding 182g of n-octanol and 0.22 g of boric acid into a reaction kettle, dropwise adding the mixed solution of the n-octanol, the methyl acrylate and the di-tert-butyl peroxide after the reaction kettle is heated to 180 ℃, continuing to react for 1.5 hours after dropwise adding, cooling after the reaction is finished, wherein the conversion rate of the methyl acrylate is 99.8 percent, and the selectivity is 82 percent.
Claims (10)
1. A preparation method of peach aldehyde comprises the following steps:
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 peach aldehyde.
2. The method according to claim 1, wherein the peroxide in step 1) 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.
3. The method according to claim 1 or 2, wherein the auxiliary agent in step 1) is one or more selected from tri-n-butyl (vinyl) tin, dibutyltin diacetate and dibutyltin maleate.
4. A process according to any one of claims 1-3, characterized in that the molar ratio of n-octanol to methyl acrylate in step 1) is 5-10, preferably 6-8.
5. The process according to any one of claims 1 to 4, characterized in that the molar ratio of methyl acrylate to peroxide in step 1) is from 10 to 20, preferably from 14 to 16, from 1.
6. The process according to any one of claims 1 to 5, characterized in that the amount of auxiliary agent used in step 1) is 0.01 to 0.5%, preferably 0.05 to 0.2% of the amount of peroxide.
7. The process according to any one of claims 1 to 6, wherein the temperature of the reaction of step 1) is 150 to 210 ℃, preferably 170 to 190 ℃; the reaction time is 15 to 120s, preferably 30 to 60s.
8. The process according to any one of claims 1 to 7, wherein after the reaction in step 1), the reaction solution is cooled at 0 to 20 ℃, preferably 5 to 10 ℃.
9. The process according to any one of claims 1 to 8, wherein in step 2), the amount of the acidic catalyst is 0.01 to 1%, preferably 0.05 to 0.2% by mass of the acid alcohol intermediate.
10. The process according to any one of claims 1 to 9, wherein the temperature of the reaction of step 2) is 110 to 180 ℃, preferably 120 to 160 ℃; the reaction residence time is 10 to 60min, preferably 15 to 30min.
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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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