CN117229132B - Synthesis method of trans-2, 4-nonadienal - Google Patents
Synthesis method of trans-2, 4-nonadienal Download PDFInfo
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- CN117229132B CN117229132B CN202311493619.6A CN202311493619A CN117229132B CN 117229132 B CN117229132 B CN 117229132B CN 202311493619 A CN202311493619 A CN 202311493619A CN 117229132 B CN117229132 B CN 117229132B
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- valeraldehyde
- crotonaldehyde
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- ZHHYXNZJDGDGPJ-GCSGCOTJSA-N (2e)-nona-2,4-dienal Chemical compound CCCCC=C\C=C\C=O ZHHYXNZJDGDGPJ-GCSGCOTJSA-N 0.000 title claims abstract description 27
- 238000001308 synthesis method Methods 0.000 title claims abstract description 13
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 239000002904 solvent Substances 0.000 claims abstract description 31
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 claims abstract description 21
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003513 alkali Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 7
- 239000007858 starting material Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000004821 distillation Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- 238000006243 chemical reaction Methods 0.000 abstract description 26
- 239000002994 raw material Substances 0.000 abstract description 8
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005580 one pot reaction Methods 0.000 abstract description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- 239000000203 mixture Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000007864 aqueous solution Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 238000010268 HPLC based assay Methods 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- ZHHYXNZJDGDGPJ-BSWSSELBSA-N (2e,4e)-nona-2,4-dienal Chemical compound CCCC\C=C\C=C\C=O ZHHYXNZJDGDGPJ-BSWSSELBSA-N 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Natural products CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000005292 vacuum distillation Methods 0.000 description 4
- ZHHYXNZJDGDGPJ-UHFFFAOYSA-N 2,4-Nonadienal Natural products CCCCC=CC=CC=O ZHHYXNZJDGDGPJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002304 perfume Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- XCWKYQWOLSOBCC-UHFFFAOYSA-N 1,1-Diethoxypentane Chemical compound CCCCC(OCC)OCC XCWKYQWOLSOBCC-UHFFFAOYSA-N 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 150000002085 enols Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000013599 spices Nutrition 0.000 description 2
- -1 vinyl diethyl ether Chemical compound 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 241000207199 Citrus Species 0.000 description 1
- 241000219112 Cucumis Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 240000008067 Cucumis sativus Species 0.000 description 1
- 235000010799 Cucumis sativus var sativus 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
- 150000001299 aldehydes Chemical class 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000020971 citrus fruits Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000895 extractive distillation Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of trans-2, 4-nonadienal, which comprises the following steps: taking n-valeraldehyde and crotonaldehyde as initial raw materials, and carrying out aldol condensation reaction in a solvent under the action of alkali. According to the synthesis method of trans-2, 4-nonadienal, n-valeraldehyde and crotonaldehyde are used as starting materials, under the action of alkali, the trans-2, 4-nonadienal can be generated through one-step reaction, the sources of the raw materials are wide, the cost is low, a high-temperature and high-pressure environment is not needed, and the reaction condition is mild; meanwhile, a strong reducing agent and a strong oxidizing agent are not used, so that the reaction safety is higher; meanwhile, the purity of the product can reach 98.1 percent, the yield can reach 87 percent, and the method is suitable for industrial production and has good application prospect.
Description
Technical Field
The invention relates to the technical field of synthesis of perfumes and medical intermediates, in particular to a synthesis method of 2, 4-nonadienal.
Background
The information disclosed in the background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an admission or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Trans-2, 4-nonadienal, also known as (E, E) -2, 4-nonadienal, having a molecular weight of 138.21, # CAS of 5910-87-2 and a molecular formula of C 9 H 14 O has a structure shown as a formula (I),
formula (I).
The 2, 4-nonadienal is an important edible spice with citrus taste, melon taste and cucumber taste, and is mainly applied to the field of food spices. At present, few reports are about the synthesis method of 2, 4-nonadienal, and a plurality of synthesis routes of 2, 4-dienal substances are reported in literature 2, 4-dienal and 2-enal perfume synthesis method research (perfume and essence cosmetics, 1998 (03): 8-11), and are all obtained through alkyne reduction and/or enol oxidation. However, there is a risk of excessive reduction and oxidation during alkyne reduction and enol oxidation, so the requirements on the catalyst and reaction conditions are severe, and the reported methods have low yields, and the total yields are lower than 60%.
Patent CN 114573437a (publication date 2022.06.03) discloses a method for producing trans-2, 4-nonadienal, which comprises the following steps: n-valeraldehyde reacts with ethanol under normal pressure under the catalysis condition to form 1, 1-diethoxypentane, 1-diethoxypentane and vinyl diethyl ether are synthesized into 1, 3-triethoxyheptane under the low temperature and catalysis condition, 1, 3-triethoxyheptane and vinyl diethyl ether are synthesized into 1,3, 5-tetraethoxynonane under the low temperature and catalysis condition, then the 1,3, 5-tetraethoxynonane is subjected to reflux hydrolysis under the condition of taking acetic acid as a solvent to obtain trans-2, 4-nonadienal, and then desolventizing and reduced pressure rectification are carried out to obtain a fine product, wherein the yield is 36%. It can be seen that the preparation process of the method is complicated and the yield is very low.
Therefore, how to obtain a synthesis method with simple reaction process, mild reaction conditions, high yield and low reagent cost has become a major problem to be solved urgently by the leading scholars in the field.
Disclosure of Invention
In view of the above, the invention provides a synthesis method of trans-2, 4-nonadienal, which has the advantages of simple operation, less three wastes, high yield and safe synthesis process, and is more suitable for industrial scale-up production.
The invention provides a synthesis method of trans-2, 4-nonadienal, which comprises the following steps:
taking n-valeraldehyde and crotonaldehyde as starting materials, and carrying out aldol condensation reaction in a solvent at 20-80 ℃ for 10-30 hours under the action of alkali to obtain the catalyst;
wherein the molar ratio of n-valeraldehyde to crotonaldehyde is 1:0.9-1.4; the alkali comprises one or more of sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, triethylamine or piperidine; the mass concentration of the alkali is 1-15%.
Preferably, the base is sodium hydroxide.
Preferably, the alkali is added in a manner of an aqueous alkali solution, wherein the addition manner is dropwise addition, and the temperature during the dropwise addition is-5 ℃.
Further preferably, the volume ratio of the aqueous alkali solution to the solvent is 1: 2-10.
Preferably, the solvent is one of methanol, ethanol, acetonitrile, tetrahydrofuran or N, N-dimethylformamide.
Further preferably, the solvent is ethanol.
Preferably, the dosage ratio of n-valeraldehyde to solvent is 20:100-300 g/mL.
Preferably, the molar ratio of the n-valeraldehyde to the crotonaldehyde is 1:1-1.2.
Preferably, the temperature of the aldol condensation reaction is 20-40 ℃; the aldol condensation reaction time is 10-20 hours.
Preferably, a post-treatment step is also included. The post-treatment step comprises the steps of sequentially carrying out distillation, extraction, vacuum concentration and reduced pressure distillation on the reacted solution to obtain the trans-2, 4-nonadienal.
Compared with the prior art, the invention has the following beneficial effects:
according to the synthesis method of trans-2, 4-nonadienal, n-valeraldehyde and crotonaldehyde are used as starting materials, under the action of alkali, the trans-2, 4-nonadienal can be generated through one-step reaction, the sources of the raw materials are wide, the cost is low, a high-temperature and high-pressure environment is not needed, and the reaction condition is mild; meanwhile, a strong reducing agent and a strong oxidizing agent are not used, so that the reaction safety is higher; meanwhile, the purity of the product is up to 98%, the highest yield can be up to about 90%, and the method is suitable for industrial production and has good application prospect.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention. It will be obvious to those skilled in the art that other figures may be obtained from these figures without the inventive effort.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of trans-2, 4-nonadienal prepared in example 1 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art. All the raw materials of the present invention are not particularly limited in purity, and analytical purity is preferably used in the present invention.
The invention provides a synthesis method of trans-2, 4-nonadienal, which comprises the following steps:
taking n-valeraldehyde and crotonaldehyde as initial raw materials, and carrying out aldol condensation reaction in a solvent under the action of alkali.
The equation for the above reaction of the present invention is shown below:
the base of the present invention is not particularly limited, and may be any base commonly used in aldol reactions known to those skilled in the art, and may be an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, potassium carbonate, or an organic base such as triethylamine and piperidine. Most preferably sodium hydroxide, the raw materials are easy to obtain, the cost is low, and the catalyst has good catalytic effect.
The concentration of the alkali in the reaction solution is 1 to 15% by mass, and more preferably 2 to 8% by mass. The alkali of the present invention is preferably added dropwise to the reaction system in the form of an aqueous alkali solution, and the temperature during the dropwise addition is-5 to 5 ℃ in order to avoid the formation of byproducts due to an excessive temperature. The volume ratio of the aqueous solution of the alkali to the solvent is 1:2 to 10, preferably 1:2.67.
The solvent is not particularly limited, and the solvent is usually used for aldol condensation reaction, which is well known to those skilled in the art, and an aqueous solution of a base is required to be added dropwise to the solvent, so that the solvent should be miscible with water for homogeneous reaction, and one of methanol, ethanol, acetonitrile, tetrahydrofuran or N, N-dimethylformamide is preferable, and ethanol is more preferable because ethanol is low in toxicity and cost, and has a good yield when used as a solvent. The solvent is not particularly limited, and the dosage of the conventional solvent for aldol condensation reaction well known to those skilled in the art is preferably 20:100-300 g/mL, and the incomplete reaction and waste caused by too much solvent can be caused by too little solvent.
The reaction conditions are not particularly limited, and the reaction conditions are conventional conditions of aldol condensation reaction well known to those skilled in the art, and can be selected and adjusted according to actual production conditions, quality requirements and product requirements, wherein the reaction temperature is preferably 20-80 ℃, more preferably 20-40 ℃, and most preferably 25 ℃; the reaction time is preferably 10 to 30 hours, more preferably 10 to 20 hours, and most preferably 12 hours. The present invention is not particularly limited in terms of other conditions of the aldol condensation reaction, and those skilled in the art can select and adjust according to actual production conditions, quality requirements, and product requirements.
The present invention also includes a post-treatment, the mode of which is not particularly limited, and the post-treatment is a post-treatment mode of such a reaction well known to those skilled in the art, and the present invention particularly preferably comprises distillation of the reacted solution to remove the solvent, extractive distillation, vacuum concentration and reduced pressure distillation to obtain trans-2, 4-nonadienal of high purity.
The molar ratio of n-valeraldehyde to crotonaldehyde is 1:0.9-1.4, and more preferably 1:1-1.2. The invention utilizes n-valeraldehyde and crotonaldehyde to carry out aldol condensation reaction, the crotonaldehyde can remove one hydrogen ion under the action of alkali, the obtained crotonaldehyde carbanion draws the conjugated olefine aldehyde of electron to be stable, and nucleophilic addition-elimination process can be well carried out with the n-valeraldehyde, thus obtaining the product of trans-nonadienal.
By adopting the technical route, the invention synthesizes the trans-2, 4-nonadienal in one step, has simple operation, wide raw material sources, low cost, no need of high-temperature and high-pressure environment and mild reaction conditions; meanwhile, a strong reducing agent and a strong oxidizing agent are not used, so that the reaction safety is higher. The reaction yield can reach 87% at most, and the final product has high purity up to 98.1%.
The technical scheme of the invention is further described below by combining specific embodiments.
Example 1
To the reaction flask were added ethanol (200 mL), n-valeraldehyde (21.5 g,0.25 mol) and crotonaldehyde (17.5 g,0.25 mol), 75 mL of a 20% aqueous NaOH solution was added dropwise at 0℃and the mixture was stirred at 25℃for 12h. The solvent was distilled off under reduced pressure, the mixture was diluted with 200 mL dichloromethane and 100 mL aqueous solution, and the separated liquid was extracted. The organic extract was concentrated in vacuo. The 98-99 ℃ (10 torr) fraction was collected by distillation under reduced pressure to give 30 g in 87% yield, purity by HPLC: 98.1%.
The obtained product is subjected to nuclear magnetic resonance hydrogen spectrum test, the nuclear magnetic resonance hydrogen spectrum is shown in figure 1, and the result is as follows:
1 H NMR (500 MHz, CDCl 3 ) δ 9.54 (d,J= 7.9 Hz, 1H), 7.09 (dd,J= 15.1, 9.5 Hz, 1H), 6.40 – 6.23 (m, 2H), 6.12 – 6.00 (m, 1H), 2.23 (dd,J= 12.8, 6.2 Hz, 2H), 1.50 – 1.42 (m, 2H), 1.40 – 1.31 (m, 2H), 0.92 (t,J= 6.9 Hz, 3H)。
example 2
To the reaction flask were added methanol (200 mL), n-valeraldehyde (21.5 g,0.25 mol) and crotonaldehyde (17.5 g,0.25 mol), 75 mL of a 20% aqueous NaOH solution was added dropwise at 0℃and the mixture was stirred at 25℃for 12h. The solvent was distilled off under reduced pressure, the mixture was diluted with 200 mL dichloromethane and 100 mL aqueous solution, and the separated liquid was extracted. Organic lifting deviceThe extract was concentrated in vacuo. Collecting 98-99 ℃ (10 torr) fraction by vacuum distillation to obtain 24 g, and obtaining 70% of the yield; HPLC assay purity: 97.6%. 1 The H NMR data are as in example 1.
Example 3
Tetrahydrofuran (200 mL), n-valeraldehyde (21.5 g,0.25 mol) and crotonaldehyde (17.5 g,0.25 mol) were added to the reaction flask, 75 mL of a 20% aqueous NaOH solution was added dropwise thereto at 0℃and the mixture was stirred at 25℃for 12h. The solvent was distilled off under reduced pressure, the mixture was diluted with 200 mL dichloromethane and 100 mL aqueous solution, and the separated liquid was extracted. The organic extract was concentrated in vacuo. Vacuum rectifying and collecting 98-99 deg.c (10 torr) fraction to obtain 16 g in 46% yield; HPLC assay purity: 96.2%. 1 The H NMR data are as in example 1.
Example 4
To the reaction flask were added ethanol (200 mL), n-valeraldehyde (21.5 g,0.25 mol) and crotonaldehyde (24.5 g,0.30 mol), 75 mL of a 20% aqueous NaOH solution was added dropwise at 0℃and the mixture was stirred at 25℃for 12h. The solvent was distilled off under reduced pressure, the mixture was diluted with 200 mL dichloromethane and 100 mL aqueous solution, and the separated liquid was extracted. The organic extract was concentrated in vacuo. Vacuum rectifying and collecting 98-99 ℃ (10 torr) fraction to obtain 28.5g, yield 82%; HPLC assay purity: 98.0%. 1 The H NMR data are as in example 1.
Example 5
Acetonitrile (200 mL), n-valeraldehyde (21.5 g,0.25 mol) and crotonaldehyde (17.5 g,0.25 mol) were added to the reaction flask, 100 mL of a 20% aqueous NaOH solution was added dropwise thereto at 0℃and the mixture was stirred at 25℃for 12h. The solvent was distilled off under reduced pressure, the mixture was diluted with 200 mL dichloromethane and 100 mL aqueous solution, and the separated liquid was extracted. The organic extract was concentrated in vacuo. Collecting 98-99 ℃ (10 torr) fraction by vacuum distillation to obtain 12 g, yield 34%; HPLC assay purity: 93.4%. 1 The H NMR data are as in example 1.
Example 6
To the reaction flask were added ethanol (200 mL), n-valeraldehyde (21.5 g,0.25 mol) and crotonaldehyde (17.5 g,0.25 mol), 75 mL of a 20% KOH aqueous solution was added dropwise at 0℃and the mixture was stirred at 25℃for 12h. The solvent was distilled off under reduced pressure, and 200 mL dichloromethane and 100 mL were usedThe mixture was diluted with aqueous solution and the extract was separated. The organic extract was concentrated in vacuo. Collecting 98-99 ℃ (10 torr) fraction by vacuum distillation to obtain 23 g, and obtaining 67% of yield; HPLC assay purity: 96.9%. 1 The H NMR data are as in example 1.
Example 7
To the reaction flask were added ethanol (200 mL), n-valeraldehyde (21.5 g,0.25 mol) and crotonaldehyde (17.5 g,0.25 mol), 75 mL of 25% aqueous NaOH solution was added dropwise at 0℃and the mixture was stirred at 25℃for 20 hours. The solvent was distilled off under reduced pressure, the mixture was diluted with 200 mL dichloromethane and 100 mL aqueous solution, and the separated liquid was extracted. The organic extract was concentrated in vacuo. Collecting 98-99 ℃ (10 torr) fraction by vacuum distillation to obtain 27 g, yield 78%; HPLC assay purity: 97.8%. 1 The H NMR data are as in example 1.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. The synthesis method of the trans-2, 4-nonadienal is characterized by comprising the following steps of:
taking n-valeraldehyde and crotonaldehyde as starting materials, and carrying out aldol condensation reaction in a solvent at 20-40 ℃ for 10-20 hours under the action of alkali to obtain the catalyst;
wherein the molar ratio of n-valeraldehyde to crotonaldehyde is 1:0.9-1.4; the base includes one or more of sodium hydroxide or potassium hydroxide; the mass concentration of the alkali is 1-15%; the solvent is methanol or ethanol.
2. The method of synthesizing trans-2, 4-nonadienal according to claim 1, wherein the base is sodium hydroxide.
3. The method for synthesizing trans-2, 4-nonadienal according to claim 1, wherein the alkali is added in the form of an aqueous alkali solution by dropping at a temperature of-5 to 5 ℃.
4. The method for synthesizing trans-2, 4-nonadienal according to claim 3, wherein the volume ratio of the aqueous alkali solution to the solvent is 1: 2-10.
5. The method of synthesizing trans-2, 4-nonadienal according to claim 1, wherein the solvent is ethanol.
6. The method for synthesizing trans-2, 4-nonadienal according to claim 1, wherein the dosage ratio of n-valeraldehyde to solvent is 20:100-300, and the unit is g/mL.
7. The method for synthesizing trans-2, 4-nonadienal according to claim 1, wherein the molar ratio of n-valeraldehyde to crotonaldehyde is 1:1-1.2.
8. The method for synthesizing trans-2, 4-nonadienal according to claim 1, further comprising a post-treatment step; the post-treatment step comprises the steps of sequentially carrying out distillation, extraction, vacuum concentration and reduced pressure distillation on the reacted solution to obtain the trans-2, 4-nonadienal.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5434313A (en) * | 1992-04-07 | 1995-07-18 | Davy Mckee (London) Limited | Aldolisation-dehydration process |
| US20050175555A1 (en) * | 2002-05-07 | 2005-08-11 | Riccardo Stradi | Polyunsaturated linear aldehydes and their derivatives with anti-radical and anti-tumoral activity |
| CN114573437A (en) * | 2022-03-21 | 2022-06-03 | 滕州市天水生物科技有限公司 | Production method of trans-2, 4-nonadienal |
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2023
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| US5434313A (en) * | 1992-04-07 | 1995-07-18 | Davy Mckee (London) Limited | Aldolisation-dehydration process |
| US20050175555A1 (en) * | 2002-05-07 | 2005-08-11 | Riccardo Stradi | Polyunsaturated linear aldehydes and their derivatives with anti-radical and anti-tumoral activity |
| CN114573437A (en) * | 2022-03-21 | 2022-06-03 | 滕州市天水生物科技有限公司 | Production method of trans-2, 4-nonadienal |
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