CN108047036A - A kind of synthetic method of Ergol - Google Patents
A kind of synthetic method of Ergol Download PDFInfo
- Publication number
- CN108047036A CN108047036A CN201711268740.3A CN201711268740A CN108047036A CN 108047036 A CN108047036 A CN 108047036A CN 201711268740 A CN201711268740 A CN 201711268740A CN 108047036 A CN108047036 A CN 108047036A
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- reaction
- ergol
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- sodium benzoate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/10—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond
- C07C67/11—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with ester groups or with a carbon-halogen bond being mineral ester groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
Abstract
The invention discloses a kind of synthetic methods of Ergol, belong to organic synthesis field.Sodium benzoate, benzyl chloride, solvent is taken to add in reaction vessel, the reaction generation Ergol under 60-100 DEG C of environment.It cools down after reaction, is removed by filtration the solid sodium chloride being precipitated in reaction solution.After solvent is evaporated off in reaction solution, excessive sodium benzoate is filtered out.Filtrate removes low-boiling-point substance in product and high-boiling components to get finished product by distillation, rectifying.This method avoid the uses of catalyst, and the reaction time is short, and reaction condition is simple, and product yield is high.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to be Ergol synthetic method
Background technology
Ergol is also known as styrax benzyl ester, is a kind of colourless or pale yellow oily liquid, has light similar apricot
The fragrance of benevolence.Ergol is commonly used for the setting agent and corrective incense agent of floral perfume, also there is more application in food flavor.It should
Product is also widely used as plasticizer or solvent, when being particularly mixed with resin in nitrocellulose, can with benzoic acid diethylester or
Dibutyl ester is used in mixed way.In addition, the product can be used for configuring pertussis medicine and control asthma medicine, there is expansion blood vessel and release convulsion
Contraction acts on, and can be used as the raw material of compound acetic acid progesterone and dimethyl phthalate.
The synthesis of Ergol there is several methods that, one kind is using benzoic acid and benzyl alcohol as raw material, in the work of catalyst
Ergol is made with lower direct esterification.Japan Patent 2002121170 is with HfCl4Complex with tetrahydrofuran is catalysis
Agent.Chinese patent 200710031101 is using supported ion liquid as catalyst.The catalyst preparation mistake that above-mentioned two patent needs
Journey is complicated, with high costs.One kind is using benzaldehyde as raw material, and Ergol is obtained by benzaldehyde direct polycondensation.It is Chinese special
Profit 03137599 and the disclosure of Japan Patent 2009280529 report this method.But above-mentioned two patent needs Al (OPh)3、
ZnCl2It is catalyst with metal-organic solution deposition etc., catalyst preparation process is complicated, and prepares Ergol reaction process by-product
Object is more.Japan Patent 2010184890 discloses one kind and directly synthesizes benzene through dioxygen oxidation under high temperature, high pressure by benzyl alcohol
The method of benzyl formate, requirement of this method to equipment is high, and byproduct of reaction is more, and product yield is low (31%).United States Patent (USP)
6281382 and Chinese patent 106883116 disclose method using toluene as the direct synthesizing benzoic acids benzyl ester of raw material.Two methods
Method is with Pd (OAc)2, Phen and iron oxide gold-supported be catalyst, Ergol is only the by-product reacted,
Product yield is low.Chinese patent 106831418 discloses a kind of method that Ergol is prepared using benzyl alcohol as raw material.It but should
Method needs to prepare catalyst with zirconium dioxide and chromium trioxide etc. for raw material, and preparation process is complicated, and reaction step is long, causes to give birth to
It produces with high costs.Chinese patent 102219662 discloses one kind and prepares benzene first as raw material using benzoic acid and toluene gas mixture
The method of acid benzyl ester, the catalyst of this method are made of the composite oxides of Zr, Cu, Al, Zn, B and rare earth element, prepare catalysis
The cost of material of agent is high, and preparation process is complicated.The reaction process of benzoic acid and toluene is complicated, severe reaction conditions, side reaction
It is more.The above method is due to there are various limitations, having no industrial applications.
It is using sodium benzoate and benzyl chloride as raw material, in catalyst to report most Ergol synthetic methods at present
Direct reaction prepares Ergol under effect, and difference is concentrated mainly in the selection of catalyst (Chinese patent
106831428；Speciality Petrochemicals, 2006,3:16；Chemistry and bioengineering, 2008,25:29；Chemistry and bonding, 2008,
30:39；Liaoming Petrochemical Univ's journal, 2007,27:21；Hunan chemical industry, 1999,29：23 etc.).This method prepares benzoic acid
During benzyl ester, solvent is added without.Because starting benzoic acid sodium and benzyl chloride intersolubility are poor, reaction often needs to add in phase transfer catalysis (PTC)
Agent.Common phase transfer catalyst has triethylamine, tetrabutylammonium bromide, triethyl benzyl ammonia chloride, cetyl trimethyl bromine
Change ammonium etc..This method needs substantial amounts of catalyst, and the reaction time is longer, and reaction temperature is higher.Therefore, in order to improve benzoic acid
Sodium and benzyl chloride reaction rate, reduce the use of phase transfer catalyst, and inventor develops one kind benzoic acid in homogeneous system
Sodium and the method for benzyl chloride reaction synthesizing benzoic acids benzyl ester.The solvent that this method is all dissolved using sodium benzoate and benzyl chloride, makes
It must react and be carried out in homogeneous system, without adding in phase transfer catalyst.With the progress of reaction, side product chlorinated sodium is in solvent
Middle precipitation, accelerates reaction rate, shortens the reaction time.
The content of the invention
The present invention overcomes the deficiencies of the prior art and provide a kind of method of no catalytic esterification synthesizing benzoic acids benzyl ester.The party
Method avoids the use of catalyst, and the reaction time is short, and reaction condition is simple, and product yield is high.
To achieve these goals, the technical solution adopted in the present invention is as follows：
A kind of method of no catalytic esterification synthesizing benzoic acids benzyl ester：Sodium benzoate, benzyl chloride, solvent is taken to add in reaction vessel
In, the reaction generation Ergol under 60-100 DEG C of environment.It cools down after reaction, is removed by filtration the chlorine being precipitated in reaction solution
Change sodium solid.After solvent is evaporated off in reaction solution, excessive sodium benzoate is filtered out.Filtrate is removed by distillation, rectifying in product
Low-boiling-point substance and high-boiling components are to get finished product.The solvent is one kind or two in N,N-dimethylformamide, chloroform, toluene or benzene
Kind combination of the above；The sodium benzoate and the molar ratio of benzyl chloride are 1-10:1；The reaction temperature is 60-100 DEG C；Institute
When the reaction time stated is 1-2 small.
In the present invention, preferred scheme is that the solvent is n,N-Dimethylformamide and toluene.
In the present invention, preferred scheme is that the molar ratio of the sodium benzoate and benzyl chloride is 1.5-2:1.
In the present invention, preferred scheme is that the reaction temperature is 70-90 DEG C.
In existing production Ergol synthetic method, sodium benzoate and benzyl chloride intersolubility are poor, anti-in order to promote
Should carry out, it is necessary to add in phase transfer catalyst in the reaction system, the reaction time is longer, and react need under the high temperature conditions into
Row, last handling process can generate the largely waste water containing phase transfer catalyst and side product chlorinated sodium.The present invention selects a kind of benzene
Sodium formate and all preferable solvent of benzyl chloride solubility so that react and carried out in homogeneous, avoid making for phase transfer catalyst
With.It is carried out due to reacting in homogeneous system, reaction time and temperature are below existing method.Further, since byproduct chlorination
Solubility is poor in a solvent for sodium, is gradually precipitated as reaction carries out sodium chloride, directly the i.e. separable byproduct sodium chloride of filtering.
In step of the present invention, reaction dissolvent, excessive sodium benzoate, side product chlorinated sodium can all realize recycling profit in anhydrous conditions
With improving resource utilization, reduce the generation of waste water.
Advantageous effect：Compared with prior art, the invention has the advantages that：
1. reaction conversion ratio and selectivity very high, benzyl chloride conversion ratio ＞ 98.1%, reaction selectivity ＞ 92%, product
Yield can reach more than 90%；Product purity is high, product purity ＞ 99.2%；
2. reaction avoids, using phase transfer catalyst, reducing production cost；
3. byproduct of reaction sodium chloride is easily recycled；
4. being easy to get using raw material, production cost is low；
5. one-step synthesis Ergol, route are simple, it is easy to accomplish industrialization.
Specific embodiment
In the embodiment of the present invention：Since front-end volatiles, end cuts and the bottom of distillation and rectifying can all take away portioned product, institute
It can not reflect actual reaction conversion ratio and product yield with the yield of final products.Therefore, the product yield of this paper uses
Following methods calculate：With gas chromatography standard curve method, the amount that crude product to be distilled contains Ergol is quantitative determined, with this
As Production rate product yield.Specific formula for calculation is as follows：
Embodiment 1
A kind of method of no catalytic esterification synthesizing benzoic acids benzyl ester：67.17g (550mmol) sodium benzoate, 63.29g
(500mmol) benzyl chloride, 200mL n,N-Dimethylformamide are added in three-necked bottle, are reacted at 80 DEG C.Just start reactant
It is white muddy shape, with the progress of heating stirring, reaction solution gradually becomes clarification.Keep 80 DEG C reaction, with reaction into
Row has in reaction solution white solid sodium chloride to be precipitated, when reaction 1.5 is small after terminate.After reaction solution is cooled to room temperature, Buchner funnel
It filters, collects filtrate.Vacuum distillation, is evaporated off the white milkiness state of solution after solvent n,N-Dimethylformamide.It is separated by filtration
The sodium benzoate solid of precipitation, filtrate remove low-boiling-point substance in product and high-boiling components to get Ergol by distillation, rectifying
Finished product, product are colourless transparent liquid, are white needle-like crystals under low temperature.It is detected using gas chromatography, product purity
For 99.38%, product yield 91.56%.The conversion ratio of benzyl chloride is 98.52%, reaction selectivity 92.93%.
Embodiment 2
A kind of method of no catalytic esterification synthesizing benzoic acids benzyl ester：91.59g (750mmol) sodium benzoate, 63.29g
(500mmol) benzyl chloride, 300mL toluene are added in three-necked bottle, are reacted at 90 DEG C.Just start the white muddiness of reaction system
Shape, with the progress of heating stirring, reaction solution gradually becomes clarification.90 DEG C of reactions are kept, with the progress of reaction, are had in reaction solution
White solid sodium chloride is precipitated, when reaction 1 is small after terminate.After reaction solution is cooled to room temperature, Buchner funnel filters, and collects filtrate.
Vacuum distillation, is evaporated off the white milkiness state of solution after solvent toluene.The sodium benzoate solid of precipitation is separated by filtration, filtrate passes through
Distillation, rectifying remove low-boiling-point substance in product and high-boiling components to get Ergol finished product, and product is colourless transparent liquid, low
Temperature is lower for white needle-like crystals.It is detected using gas chromatography, product purity 99.42%, product yield 93.16%.
The conversion ratio of benzyl chloride is 98.94%, reaction selectivity 94.16%.
Embodiment 3
A kind of method of no catalytic esterification synthesizing benzoic acids benzyl ester：109.91g (900mmol) sodium benzoate, 75.94g
(600mmol) benzyl chloride, 500mL chloroforms are added in three-necked bottle, are heated to reflux.Just start the white muddy shape of reaction system, with
The progress of heating stirring, reaction solution gradually becomes clarification.It maintains the reflux for, with the progress of reaction, has white chlorination in reaction solution
Sodium solid be precipitated, reaction 2 it is small when after terminate.After reaction solution is cooled to room temperature, Buchner funnel filters, and collects filtrate.Vacuum distillation,
The white milkiness state of solution after solvent chloroform is evaporated off.The sodium benzoate solid of precipitation is separated by filtration, filtrate passes through distillation, rectifying
Remove low-boiling-point substance in product and high-boiling components to get Ergol finished product, product is colourless transparent liquid, is white under low temperature
Acicular crystal.It is detected using gas chromatography, product purity 99.31%, product yield 92.69%.Benzyl chloride turns
Rate is 98.81%, reaction selectivity 93.80%.
Embodiment 4
A kind of method of no catalytic esterification synthesizing benzoic acids benzyl ester：244.24g (2mol) sodium benzoate, 126.58g
(1mol) benzyl chloride, 700mL benzene are added in three-necked bottle, are heated to reflux.The white muddy shape of reaction system is just started, with heating
The progress of stirring, reaction solution gradually become clarification.It maintains the reflux for reacting, with the progress of reaction, has white sodium chloride in reaction solution
Solid be precipitated, reaction 1 it is small when after terminate.After reaction solution is cooled to room temperature, Buchner funnel filters, and collects filtrate.Vacuum distillation is steamed
Except the white milkiness state of solution after solvent benzol.The sodium benzoate solid of precipitation is separated by filtration, filtrate is removed by distillation, rectifying
For low-boiling-point substance and high-boiling components in product to get Ergol finished product, product is colourless transparent liquid, is white needles under low temperature
Crystal.It is detected using gas chromatography, product purity 99.38%, product yield 94.37%.The conversion ratio of benzyl chloride
For 99.14%, reaction selectivity 95.19%.
The embodiment above is only the preferred embodiments of the invention, it is impossible to for limiting the scope of protection of the invention, this
The variation and replacement for any unsubstantiality that field technology personnel are done on the basis of the present invention belong to claimed
Scope.
Claims (8)
1. a kind of synthetic method of Ergol, it is characterised in that：Sodium benzoate, benzyl chloride, solvent are in 60-100 DEG C of environment
It is lower reaction generation Ergol, cool down after reaction, filter, after solvent is evaporated off in reaction solution, filtering, filtrate by distillation,
Rectifying is up to Ergol；The solvent is one or more kinds of in N,N-dimethylformamide, chloroform, toluene or benzene
Combination.
2. synthetic method according to claim 1, it is characterised in that：The sodium benzoate and the molar ratio of benzyl chloride are
1‐10:1；The reaction temperature is 60-100 DEG C；When the reaction time is 1-2 small.
3. synthetic method according to claim 1 or 2, it is characterised in that：The solvent is N,N-dimethylformamide
And toluene.
4. synthetic method according to claim 1 or 2, it is characterised in that：The molar ratio of the sodium benzoate and benzyl chloride
For 1.5-2:1.
5. synthetic method according to claim 3, it is characterised in that：The molar ratio of the sodium benzoate and benzyl chloride is
1.5‐2:1。
6. according to the synthetic method described in claim 1 or 2 or 5, it is characterised in that：The reaction temperature is 70-90 DEG C.
7. synthetic method according to claim 3, it is characterised in that：The reaction temperature is 70-90 DEG C.
8. synthetic method according to claim 4, it is characterised in that：The reaction temperature is 70-90 DEG C.
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| CN201711268740.3A CN108047036A (en) | 2017-12-05 | 2017-12-05 | A kind of synthetic method of Ergol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109160880A (en) * | 2018-10-29 | 2019-01-08 | 淮安万邦香料工业有限公司 | A kind of preparation method of ethyl benzoate |
| CN109232244A (en) * | 2018-10-29 | 2019-01-18 | 淮安万邦香料工业有限公司 | A kind of preparation method of benzyl butyrate |
| CN110903187A (en) * | 2018-09-15 | 2020-03-24 | 天津大加化工有限公司 | Production process of benzyl benzoate |
| CN111675617A (en) * | 2020-06-24 | 2020-09-18 | 湖北葛店人福药用辅料有限责任公司 | Synthesis method of benzyl benzoate |
| CN111978179A (en) * | 2020-08-27 | 2020-11-24 | 青岛科技大学 | Synthetic method of 6-hydroxyhexanoate |
| CN115160132A (en) * | 2022-08-06 | 2022-10-11 | 天津大加化工有限公司 | Production process of benzyl benzoate |
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| RU2128162C1 (en) * | 1997-07-16 | 1999-03-27 | Казымов Александр Васильевич | Method of preparing benzyl benzoate |
| CN106831428A (en) * | 2017-01-23 | 2017-06-13 | 天津东大化工集团有限公司 | A kind of method of low temperature synthesizing benzoic acids benzyl ester |
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2017
- 2017-12-05 CN CN201711268740.3A patent/CN108047036A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2128162C1 (en) * | 1997-07-16 | 1999-03-27 | Казымов Александр Васильевич | Method of preparing benzyl benzoate |
| CN106831428A (en) * | 2017-01-23 | 2017-06-13 | 天津东大化工集团有限公司 | A kind of method of low temperature synthesizing benzoic acids benzyl ester |
Non-Patent Citations (1)
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| 易封萍等: "《合成香料工艺学》", 31 May 2016, 中国轻工业出版社 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110903187A (en) * | 2018-09-15 | 2020-03-24 | 天津大加化工有限公司 | Production process of benzyl benzoate |
| CN110903187B (en) * | 2018-09-15 | 2022-05-13 | 天津大加化工有限公司 | Production process of benzyl benzoate |
| CN109160880A (en) * | 2018-10-29 | 2019-01-08 | 淮安万邦香料工业有限公司 | A kind of preparation method of ethyl benzoate |
| CN109232244A (en) * | 2018-10-29 | 2019-01-18 | 淮安万邦香料工业有限公司 | A kind of preparation method of benzyl butyrate |
| CN111675617A (en) * | 2020-06-24 | 2020-09-18 | 湖北葛店人福药用辅料有限责任公司 | Synthesis method of benzyl benzoate |
| CN111675617B (en) * | 2020-06-24 | 2023-04-04 | 湖北葛店人福药用辅料有限责任公司 | Synthesis method of benzyl benzoate |
| CN111978179A (en) * | 2020-08-27 | 2020-11-24 | 青岛科技大学 | Synthetic method of 6-hydroxyhexanoate |
| CN115160132A (en) * | 2022-08-06 | 2022-10-11 | 天津大加化工有限公司 | Production process of benzyl benzoate |
| CN115160132B (en) * | 2022-08-06 | 2023-10-31 | 天津大加化工有限公司 | Production process of benzyl benzoate |
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Application publication date: 20180518 |