CN104774190A - Preparation method of perfume-grade fructone - Google Patents
Preparation method of perfume-grade fructone Download PDFInfo
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- CN104774190A CN104774190A CN201510199589.7A CN201510199589A CN104774190A CN 104774190 A CN104774190 A CN 104774190A CN 201510199589 A CN201510199589 A CN 201510199589A CN 104774190 A CN104774190 A CN 104774190A
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- reaction
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- ethylene glycol
- apple ester
- vitriol oil
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/14—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D317/30—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Fats And Perfumes (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a preparation method of perfume-grade fructone, comprising the following steps: firstly adding raw materials (ethyl acetoacetate and ethylene glycol) in a reaction container; and then adding concentrated sulfuric acid serving as a catalyst and reacting to produce fructone. According to the preparation method, in the absence of a water carrying agent, esterification reaction can be carried out normally in the production process, the consumption of raw materials and auxiliary materials can be reduced, the energy consumption can be lowered, the reaction time can be shortened and the product fragrance can be improved.
Description
Technical field
The present invention relates to a kind of preparation method of apple ester, in particular for the preparation method of the apple ester of spices.
Background technology
Apple ester, also known as ethyl acetoacetate ethylene glycol ketal, is a kind of synthetic perfume, has fresh apple fragrance, is mainly used in the preparation fragrance of a flower and fruit flavour type essence.
According to " synthetic perfume technical manual " (China Light Industry Press, July in 2000 the 1st edition, Liu Shuwen writes, 345 pages), apple ester preparation method is employing methyl aceto acetate, ethylene glycol is raw material, and under a small amount of an acidic catalyst exists, in solvent, reflux azeotropic dehydration forms.Existing production technique adopts methyl aceto acetate, ethylene glycol under an acidic catalyst condition, adds solvent, is reacted by heating.
" catalyzing and synthesizing the novel process research of apple ester " (author: Kang Wentong, Chen Qi, Hebei University of Science and Technology's chemistry and pharmaceutical engineering institute in " Sichuan chemical industry and corrosion control " (the 6th phase the 5th volume in 2002); Jiao Lingxia, Hebei Medical University; Zhang Huifang, chemical plant, Shijiazhuang) in a literary composition, disclose and adopt methyl aceto acetate, ethylene glycol is raw material, add solvent hexanaphthene, uses organic acid is catalyzer, reflux 5-6 hour must finished product.
" catalyst research of synthesizing apple ester " (author Yang Shuijin in " fragrance flavor and cosmetic " (phase February the 1st in 2003), Hubei Normal University's chemistry and environment engineering) discuss the impact of multiple catalysts on synthesizing apple ester technique in a literary composition, each technique mostly uses solvent and water entrainer, such as hexanaphthene, benzene, toluene, reflux, reaction times 1.5-6.5 hour is not etc.
In above-mentioned common apple ester preparation method, reaction must use water entrainer, and can increase consumption the energy, and these water entrainer itself have smell, can affect the fragrance of the finished product, and in addition, technical process is also more complicated.
Summary of the invention
The object of this invention is to provide a kind of preparation method of spices level apple ester, the method is without under the condition of water entrainer, can not only ensure that the esterification in production process is normally carried out, and reduce consumption of raw and auxiliary materials, reduce energy consumption, Reaction time shorten, improve product fragrance.
For achieving the above object, the present invention adopts following technical scheme: a kind of preparation method of spices level apple ester, comprises the following steps: first in reaction vessel, add raw material methyl aceto acetate and ethylene glycol; Add the vitriol oil again as catalyzer, after reaction, generate apple ester.
The reaction generating apple ester is esterification, and esterification is typical reversible reaction.Speed of response is directly proportional to reactant concn, is inversely proportional to production concentration, and therefore for effectively advancing reaction to carry out to positive reaction direction, in the past conventional method is that reaction product water is taken out of reaction system with water entrainer at any time.But the water generated due to this reaction is less, and general reaction method needs heating, and under 80-150 DEG C of condition, water has certain solvability in water entrainer, causes water cannot be taken out of reaction system completely, therefore reaction not exclusively, and speed of response is slow.Principle of the present invention is by not using water entrainer, adds reactant concn, and water can be separated with water-absorbent by the strongly-acid of the vitriol oil in addition, thus promotes that molecular balance carries out to positive reaction direction.
Further preferably, the mass ratio of wherein said methyl aceto acetate, ethylene glycol, the vitriol oil is (8 ~ 12.5): (7 ~ 10.5): (1).
Ratio in this preferred version can improve the productive rate of apple ester.
Further preferably, the described concrete grammar adding methyl aceto acetate, ethylene glycol and the vitriol oil in reaction vessel is: first in reaction vessel, add methyl aceto acetate, add ethylene glycol under agitation, continue slowly to add the catalyzer vitriol oil under agitation;
Described reaction carries out 0.5-1 hour under agitation.
Further preferably, staticly treats feed liquid layering after reaction, layering feed liquid is separated, obtains apple ester crude product, more described apple ester crude product is carried out wash, fractionation obtains apple ester finished product after purifying.
Beneficial effect of the present invention at least comprises the following aspects:
1, the present invention uses the vitriol oil for catalyzer, not only plays katalysis, and plays water sorption;
2, reaction process of the present invention is without the need to heating, belongs to normal-temperature reaction, decreases energy consumption, also correspondingly simplifies operation steps and eliminates heating installation.Because temperature of reaction of the present invention is low, the time is short, and greatly reduce by product and produce, can reach fragrance by a fractionation pure, be fresh apple delicate fragrance.Avoid in the past in universal method due to high temperature, causing ethylene glycol polymer and methyl aceto acetate to react and generate by product, thus affect fragrance, as used as spices level, also needing repeatedly fractionation to purify, increase energy consumption, prolongation man-hour;
3, the present invention is without water entrainer (such as the toxic substance such as benzene, toluene), avoids this type of material residual in product, improves Product Safety, the reaction times is also greatly reduced;
4, the feed liquid of layering in the present invention, be respectively apple ester crude product and complete raw material methyl aceto acetate, the vitriol oil and the water of unreacted, follow-up, apple ester crude product and the complete raw material methyl aceto acetate of unreacted are carried out fractionation purification, its Raw methyl aceto acetate can be recycled again.And recycle without the need to by distillation, only need be separated after feed liquid static layering, without additional energy source consumption.
Embodiment
Following embodiment is only the exemplary illustration to technical scheme of the present invention, and should not be considered as of the present invention all or the restriction be considered as the technology of the present invention or restriction.
First embodiment
1, raw material: methyl aceto acetate (content >=98%) 630 grams; Ethylene glycol (content >=99%) 540 grams.
2, catalyzer: the vitriol oil (content >=98%) 63 grams.
3, preparation process:
In reaction vessel, add methyl aceto acetate, under agitation (stirring velocity 150 revs/min, stirring can allow reactant mix fully, so that reaction completes fast, but concrete stirring velocity is little on reaction impact.) adding ethylene glycol, ethylene glycol finishes rear continuation and slowly adds the vitriol oil under agitation, and now initial reaction temperature is 30 DEG C, and the vitriol oil finishes rear temperature and reaches 44 DEG C.In the present embodiment, initial reaction temperature is only the observed value of this secondary response, and during actual production, residing Normal Environmental Temperature all can react, and nonessential heating or be cooled to 30 degree, following examples are also like this.Continue to stir, react after 1 hour, static, treat that feed liquid is divided into two-layer up and down.Upper strata is methyl aceto acetate, apple ester crude mixture, obtains 736 grams (ester contents 64.23%).Lower floor is the mixed solution of ethylene glycol, the vitriol oil, water, totally 498.5 grams.
After the mixture separation of upper strata, carry out washing, fractionation, to obtain apple ester finished product 424.5 grams altogether, content 98.9%.
Second embodiment
1, raw material: methyl aceto acetate (content >=98%) 420 grams; Ethylene glycol (content >=99%) 350 grams.
2, catalyzer: the vitriol oil (content >=98%) 34 grams.
3, preparation process:
Methyl aceto acetate is added in reaction vessel, under agitation (150 revs/min) add ethylene glycol, ethylene glycol finishes rear continuation and slowly adds the vitriol oil under agitation, now initial reaction temperature is 30 DEG C, the vitriol oil finishes rear temperature and reaches 46 DEG C, continues to stir, and reacts after 0.75 hour, static, treat that feed liquid is divided into two-layer up and down.Upper strata is methyl aceto acetate, apple ester crude mixture, obtains 485 grams (ester contents 62.23%).Lower floor is the mixed solution of ethylene glycol, the vitriol oil, water, totally 315 grams.
After the mixture separation of upper strata, carry out washing, fractionation, to obtain apple ester finished product 275.5 grams altogether, content 99.1%.
3rd embodiment
1, raw material: methyl aceto acetate (content >=98%) 420 grams; Ethylene glycol (content >=99%) 357 grams.
2, catalyzer: the vitriol oil (content >=98%) 50 grams.
3, preparation process:
Methyl aceto acetate is added in reaction vessel, under agitation (150 revs/min) add ethylene glycol, ethylene glycol finishes rear continuation and slowly adds the vitriol oil under agitation, now initial reaction temperature is 30 DEG C, the vitriol oil finishes rear temperature and reaches 48 DEG C, continues to stir, and reacts after 0.5 hour, static, treat that feed liquid is divided into two-layer up and down.Upper strata is methyl aceto acetate, apple ester crude mixture, obtains 486.2 grams (ester contents 62.33%).Lower floor is the mixed solution of ethylene glycol, the vitriol oil, water, totally 316 grams.
After the mixture separation of upper strata, carry out washing, fractionation, to obtain apple ester finished product 276.1 grams altogether, content 99.01%.
As can be seen from the above-described embodiment, temperature of reaction of the present invention is low, and initial reaction temperature is only about 30 degree, is normal-temperature reaction, after the vitriol oil finishes, improves temperature, do not need extra heating because strong sulfuric acid response produces heat.In addition, the reaction times is also shorter, is only 0.5-1 hour, and in previous methods the reaction times usually need 5-6 hour.
Claims (4)
1. a preparation method for spices level apple ester, is characterized in that, comprises the following steps:
First in reaction vessel, raw material methyl aceto acetate and ethylene glycol is added;
Add the vitriol oil again as catalyzer, after reaction, generate apple ester.
2. the preparation method of a kind of spices level apple ester according to claim 1, is characterized in that: the mass ratio of wherein said methyl aceto acetate, ethylene glycol, the vitriol oil is (8 ~ 12.5): (7 ~ 10.5): (1).
3. the preparation method of a kind of spices level apple ester according to claim 1 and 2, it is characterized in that, the described concrete grammar adding methyl aceto acetate, ethylene glycol and the vitriol oil in reaction vessel is: first in reaction vessel, add methyl aceto acetate, add ethylene glycol under agitation, continue slowly to add the catalyzer vitriol oil under agitation;
Described reaction carries out 0.5-1 hour under agitation.
4. the preparation method of a kind of spices level apple ester according to claim 3, it is characterized in that: reaction is static afterwards treats feed liquid layering, layering feed liquid is separated, obtains apple ester crude product, more described apple ester crude product is carried out wash, fractionation obtains apple ester finished product after purifying.
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| CN201510199589.7A CN104774190A (en) | 2015-04-24 | 2015-04-24 | Preparation method of perfume-grade fructone |
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| CN201510199589.7A CN104774190A (en) | 2015-04-24 | 2015-04-24 | Preparation method of perfume-grade fructone |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423597A (en) * | 2019-08-09 | 2019-11-08 | 北京培康佳业技术发展有限公司 | Modified ketal of a kind of nanometer of sealing agent and preparation method thereof and oil field drilling fluids |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157047A (en) * | 2007-09-20 | 2008-04-09 | 南京化工职业技术学院 | A solid catalyst for synthesizing apple ester as well as its preparing method and application |
-
2015
- 2015-04-24 CN CN201510199589.7A patent/CN104774190A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101157047A (en) * | 2007-09-20 | 2008-04-09 | 南京化工职业技术学院 | A solid catalyst for synthesizing apple ester as well as its preparing method and application |
Non-Patent Citations (1)
| Title |
|---|
| 杨春霞等: "氨基磺酸作催化剂合成苹果酯的研究", 《辽宁化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110423597A (en) * | 2019-08-09 | 2019-11-08 | 北京培康佳业技术发展有限公司 | Modified ketal of a kind of nanometer of sealing agent and preparation method thereof and oil field drilling fluids |
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Application publication date: 20150715 |