CN105085209B - A kind of preparation method of high-purity cocker aldehyde - Google Patents
A kind of preparation method of high-purity cocker aldehyde Download PDFInfo
- Publication number
- CN105085209B CN105085209B CN201510557304.2A CN201510557304A CN105085209B CN 105085209 B CN105085209 B CN 105085209B CN 201510557304 A CN201510557304 A CN 201510557304A CN 105085209 B CN105085209 B CN 105085209B
- Authority
- CN
- China
- Prior art keywords
- aldehyde
- cocker
- purity
- preparation
- low
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 10
- 238000002360 preparation method Methods 0.000 title claims description 13
- 125000002346 iodo group Chemical group I* 0.000 claims abstract description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000005292 vacuum distillation Methods 0.000 claims description 9
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical group [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- 235000009518 sodium iodide Nutrition 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004821 distillation Methods 0.000 abstract 1
- 150000001299 aldehydes Chemical class 0.000 description 31
- 238000004587 chromatography analysis Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 244000299461 Theobroma cacao Species 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 235000009470 Theobroma cacao Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 238000006317 isomerization reaction Methods 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 235000005764 Theobroma cacao ssp. cacao Nutrition 0.000 description 1
- 235000005767 Theobroma cacao ssp. sphaerocarpum Nutrition 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 235000001046 cacaotero Nutrition 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 238000007697 cis-trans-isomerization reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 235000012907 honey Nutrition 0.000 description 1
- -1 isopentyl aldehyde Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 235000014571 nuts Nutrition 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229940100595 phenylacetaldehyde Drugs 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
Abstract
The invention discloses using low-purity cocker aldehyde as raw material, after being mixed with organic acid solvent, the catalysis of iodo salt is added, with being reacted 13 hours at a temperature of 30~100 DEG C, scrubbed, distillation produces high-purity cocker aldehyde.The cocker aldehyde purity that this manufacture method is obtained is high and old low, simple to operate, prepared by the high-purity that can be widely applied to cocker aldehyde.
Description
Technical field
The present invention relates to a kind of preparation method of high-purity compound, more particularly to a kind of preparation side of high-purity cocker aldehyde
Method.
Background technology
Cocker aldehyde, also known as trans -5- methyl -2- phenyl -2- hexenoic aldehydes, molecular formula：C13H16O；(CH3) 2CHCH2CH=
C (C6H5) CHO, structural formula is as follows：
In bitter cocoa, nut, honey, baking and green grass fragrance, natural product are present in the volatility thing for frying peanut and cocoa
In matter.Used mainly for preparation chocolate essence and cacao essence.
Cocker aldehyde can carry out aldol condensation by phenylacetaldehyde and isopentyl aldehyde and obtain, and it has cis and trans isomers, and suitable, anteiso-
Structure body ratio is about 1:9, the low-purity cocker aldehyde of content 90% or so is obtained through simple distillation, must can be contained through further rectifying purifying
95% or so finished product is measured, but its purity is still relatively low, it is impossible to meet the demand in market.Because cis-trans-isomer boiling point is high and boiling
Point is approached, therefore, and industry at present separates cis and trans isomers using rectifying, and raising finished product purity is extremely difficult, and yield rate is low, system
Cause high.
Above-mentioned cis-trans isomerization is a kind of important stereo-isomerism, and influence of the cocker aldehyde configuration to spices fragrance is very
Greatly, thus cis-trans-isomer configuration conversion be increasingly subject to research attention, pass through configuration conversion improve product quality.On double
The conversion of key configuration mainly includes three kinds of light isomery, hot isomery and catalytic isomerization, and wherein catalytic isomerization is increasingly by vast research
Person must pay attention to.
The content of the invention
It is an object of the invention to provide a kind of preparation method of high-purity cocker aldehyde, solve existing cocker aldehyde preparation method and obtain
The cocker aldehyde purity obtained is low, and further extracts difficulty greatly, the problem of cost is high.
The present invention solve technical problem technical scheme be：A kind of preparation method of high-purity cocker aldehyde, can with low-purity
Card aldehyde is raw material, after being mixed with organic acid solvent, adds the catalysis of iodo salt, with being reacted 1-3 hours at a temperature of 30~100 DEG C,
High-purity cocker aldehyde is produced through cooling washing, vacuum distillation.The mass ratio of the low-purity cocker aldehyde, organic acid and iodo salt is
100:100:0.1~1.
It is preferred that, the iodo salt is sodium iodide or KI.
It is preferred that, the organic acid is one kind in formic acid, acetic acid, propionic acid, butyric acid.
Compared with prior art, the present invention using the method for chemical catalysis by the syn-isomerism in existing low-purity cocker aldehyde
Body is converted into transisomer, so as to improve the purity of cocker aldehyde.The cocker aldehyde purity obtained by this method can reach
More than 98%, it disclosure satisfy that the demand of in the market.And this method reaction environment is simple, production and processing is convenient, and cost is low.
Embodiment
The present invention is described in further detail below by embodiment, but is not intended to limit the present invention.
Iodo salt used is that domestic analysis is pure in the present invention, is purchased from Chemical Reagent Co., Ltd., Sinopharm Group；Content
90% cocker aldehyde is directly from market purchasing.
Instrument of the present invention：GC-1690 gas chromatographs (Hangzhou section dawn chemical industry experimental instruments and equipment limited)
A kind of high-purity cocker aldehyde preparation method, in flask with three necks,round bottom, add iodo salt, 90% content cocker aldehyde,
Etc. quality organic acid, controlling reaction temperature is 30~100 DEG C, is reacted 1~3 hour, chromatogram tracking analysis.Work as cis and trans isomers
Than less than 2:98, reaction.Solvent is recovered under reduced pressure, residue uses general separation method, through cooling washing, is distilled in vacuum to give
Product, gas chromatographic analysis measures the content of cocker aldehyde more than 98%.Cooling cleaning function is to reduce significant loss, is removed residual
Stay solvent,；Because cocker aldehyde boiling point is high, using vacuum distillation, boiling point is reduced.
Embodiment 1：
A kind of preparation method of high-purity cocker aldehyde, justifies in a 250ml equipped with thermometer, stirring and reflux condensate device
In the flask of bottom, 0.2g sodium iodides, the cocker aldehyde of 100g contents 90% and 100 grams of acetic acid are added, stirs and evenly mixs, 2 is reacted at 60 DEG C
Hour, show that cis-content is less than 1% by gas chromatographic analysis.Acetic acid, cooling washing, vacuum distillation are reclaimed in vacuum distillation,
81-83 DEG C/1mmHg cut 95g are collected, the content that gas chromatographic analysis measures cocker aldehyde is 98%.
Embodiment 2：
A kind of preparation method of high-purity cocker aldehyde, justifies in a 250ml equipped with thermometer, stirring and reflux condensate device
In the flask of bottom, 0.3g KIs, the cocker aldehyde of 100g contents 90% and 100 grams of acetic acid are sequentially added, are reacted at stirring and 80 DEG C
Time is 1h, and gas chromatographic analysis shows that cis-content is less than 1%.Acetic acid, cooling washing, vacuum distillation are reclaimed in vacuum distillation,
81-83 DEG C/1mmHg cut 95g are collected, the content that gas chromatographic analysis measures cocker aldehyde is 98.2%.
Embodiment 3：
A kind of preparation method of high-purity cocker aldehyde, justifies in a 250ml equipped with thermometer, stirring and reflux condensate device
In the flask of bottom, 0.2g sodium iodides, the cocker aldehyde of 100g contents 90% and 100 grams of propionic acid are sequentially added, are reacted at stirring and 70 DEG C
Time is 3h, and gas chromatographic analysis shows that cis-content is less than 1%.Propionic acid, cooling washing, vacuum distillation are reclaimed in vacuum distillation,
81-83 DEG C/1mmHg cut 94g are collected, the content that gas chromatographic analysis measures cocker aldehyde is 98.4%.
Claims (1)
1. a kind of preparation method of high-purity cocker aldehyde, it is characterised in that：Using low-purity cocker aldehyde as raw material, with organic acid solvent
After mixing, the catalysis of iodo salt is added, with being reacted 1-3 hours at a temperature of 60~80 DEG C, height is produced through cooling washing, vacuum distillation
Purity cocker aldehyde；
The iodo salt is sodium iodide or KI；
The organic acid is the mixture of one or both of acetic acid or propionic acid；
The mass ratio of the low-purity cocker aldehyde, organic acid and iodo salt is 100:100:0.1~1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510557304.2A CN105085209B (en) | 2015-09-02 | 2015-09-02 | A kind of preparation method of high-purity cocker aldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510557304.2A CN105085209B (en) | 2015-09-02 | 2015-09-02 | A kind of preparation method of high-purity cocker aldehyde |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105085209A CN105085209A (en) | 2015-11-25 |
| CN105085209B true CN105085209B (en) | 2017-10-13 |
Family
ID=54566646
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510557304.2A Active CN105085209B (en) | 2015-09-02 | 2015-09-02 | A kind of preparation method of high-purity cocker aldehyde |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105085209B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115466172A (en) * | 2022-08-30 | 2022-12-13 | 绵阳市斯麦尔顾生物科技有限公司 | Preparation method of spice cocaldehyde |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3754038A (en) * | 1970-11-23 | 1973-08-21 | Int Flavors & Fragrances Inc | 2-phenyl-2-alkenals |
| US3970701A (en) * | 1973-07-30 | 1976-07-20 | International Flavors & Fragrances Inc. | Lower alkenals |
-
2015
- 2015-09-02 CN CN201510557304.2A patent/CN105085209B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105085209A (en) | 2015-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Kopecky et al. | Preparation of dipivaloylmethane | |
| CN102197014A (en) | Manufacture of gamma-delta-unsaturated ketones | |
| TWI422581B (en) | 2-methyl-3-(3,4-methylenedioxyphenyl) propionaldehyde and a process for producing the same | |
| CN105085209B (en) | A kind of preparation method of high-purity cocker aldehyde | |
| CN101133067A (en) | Diarylphenoxy aluminum compounds | |
| EP2985338B1 (en) | Fragrance composition and method for producing same | |
| CN115650832A (en) | Synthetic method of 2, 4-dichloro-5-fluoroacetophenone | |
| CN103342632A (en) | Method for separating high-purity cinnamyl aldehyde and cinnamyl acetate from cinnamon oil | |
| RU2667527C2 (en) | Method for preparation of 3-heptanol from mixture containing 2-ehthylhexanal and 3-heptyl formate | |
| US20100222606A1 (en) | Method for producing bisabolol which is farnesol free or is low in farnesol | |
| CN112898156B (en) | Method for recovering 1- (3, 3-dimethylcyclohexyl) ethanol and method for preparing musk eden | |
| CN104744406A (en) | Method for preparing epoxy caryophyllene from heavy turpentine oil and separating longifolene | |
| CN111302919A (en) | Method for synthesizing high-content dihydrojasmone spice | |
| CN103819329B (en) | Preparation method for 3-chloropropionylchloride | |
| CN101735263B (en) | Preparation method of ethyl trimethoxy silane | |
| JPS5826330B2 (en) | Method for producing stereo-regulated farnesyl acetate | |
| CN209128342U (en) | A kind of reaction unit being lower than raw material for product boiling point | |
| CN109096047B (en) | Preparation method of (1R) -1, 3-diphenyl-1-propanol | |
| CN202951269U (en) | High-purity fluorinated ethyl acetoacetate purifying device | |
| JPS5855129B2 (en) | Method for producing 2-substituted or unsubstituted geranyl acetates | |
| CN111635311B (en) | Preparation method of pyrinol ester | |
| CN212128031U (en) | Production device for synthesizing dihydro jasmone spice by solid acid catalysis | |
| JP4100007B2 (en) | Method for purifying cyclopentenolones | |
| Bornstein et al. | Aldolization of 1, 1-Diphenylpropanone by Grignard Reagents1 | |
| US20180105490A1 (en) | Processes for the preparation of unsaturated malonates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address | ||
| CP03 | Change of name, title or address |
Address after: No. 24, Weiyi Road, She County Circular Economy Park, Mount Huangshan City, Anhui Province 245000 Patentee after: Mount Huangshan Kehong Biotechnology Co.,Ltd. Country or region after: China Address before: No. 24, Weiyi Road, She County Circular Economy Park, Mount Huangshan City, Anhui Province 245000 Patentee before: HUANGSHAN KEHONG BIO-FLAVORS CO.,LTD. Country or region before: China |