EP1622859A1 - Method for producing a benzoate - Google Patents
Method for producing a benzoateInfo
- Publication number
- EP1622859A1 EP1622859A1 EP04730508A EP04730508A EP1622859A1 EP 1622859 A1 EP1622859 A1 EP 1622859A1 EP 04730508 A EP04730508 A EP 04730508A EP 04730508 A EP04730508 A EP 04730508A EP 1622859 A1 EP1622859 A1 EP 1622859A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- benzoic acid
- alcohol
- reaction
- acid component
- tin
- 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.)
- Withdrawn
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Definitions
- the invention relates to a method for producing a benzoic acid ester by reacting a benzoic acid component with alcohol in the presence of a catalyst.
- the invention is particularly suitable for the production of fatty acid esters of benzoic acid, which are used, for example, as base materials in cosmetics.
- Such benzoic acid esters are described, for example, in U.S. Patents 4,275,222 and 4,791,097. Either methanesulfonic acid or tin oxalate is used as the catalyst for the reaction of the benzoic acid with the corresponding alcohol. After the esterification reaction, the product obtained must be washed several times for cleaning. The overall reactions are therefore relatively complex and the yield is unsatisfactory.
- the invention thus relates to a process for the preparation of a benzoic acid ester by reacting a benzoic acid component selected from benzoic acid or a benzoic acid ester with alcohol in the presence of a catalyst which, according to the invention, is a combination of tin (II) oxide and is a phosphorus (1) compound.
- Phosphorus (I) compounds preferred according to the invention are phosphorus (I) acid (ie phosphinic acid, hypophosphorous acid) or salts of phosphorus (I) acid (phosphinates, hypophosphites).
- the catalyst used according to the invention leads to high conversion rates and high yields of very pure end product.
- the benzoic acid ester obtained can generally be used without further purification steps.
- the products obtained by the process according to the invention are distinguished by low acid numbers, water-clear colors and a weak intrinsic odor. They are therefore particularly suitable for use in cosmetic preparations.
- the alcohol which can be used in the esterification process according to the invention is not particularly limited. However, the process according to the invention is preferably used for the esterification of fatty alcohols or hydroxyfatty alcohols. Both natural and synthetic fatty alcohols can be used here.
- the alcohols can be saturated or unsaturated, branched or unbranched. Alcohols with a chain length of 6 to 22 carbon atoms, in particular 8 to 18 and particularly preferably 12 to 15 carbon atoms, are preferred. Mixtures of several of these alcohols can also be used. Suitable alcohol mixtures are obtainable for example under the brand name Neodol ® by Shell Chemical Company, Houston, Texas, in the trade.
- Preferred alcohols in the esterification process according to the invention are linear primary alcohols. Ethoxylated and / or propoxylated fatty alcohols or glycols such as propylene glycol or dipropylene glycol can also be used in the process.
- the alcohol is usually used in excess of the benzoic acid component.
- a molar excess of 10 to 30% of the alcohol over the benzoic acid component is suitable.
- Benzoic acid itself is used as the preferred benzoic acid component of the invention.
- a benzoic acid ester in a transesterification reaction.
- Esters of benzoic acid with lower alcohols are advantageously used, which can be distilled off from the reaction mixture during the esterification, if appropriate under reduced pressure.
- the methyl ester of benzoic acid is therefore preferably used.
- step (A) the reaction of the benzoic acid component with alcohol is initially carried out in a first step, hereinafter referred to as step (A), takes place at normal pressure with heating.
- the reaction under normal pressure prevents the benzoic acid component from subliming out of the reaction mixture.
- the starting material would thus not be available for the esterification and would lead to a reduced yield.
- step (B) the esterification can therefore be continued in a second step, hereinafter referred to as step (B), at elevated temperature under reduced pressure.
- step (B) leads to the completion of the esterification reaction.
- the esterification reaction is ended in a high vacuum at elevated temperature in a subsequent step (C).
- step (C) the esterification of the benzoic acid component with alcohol is practically completely completed and the excess alcohol is removed from the reaction mixture by distillation. The alcohol recovered can be used again in a subsequent reaction.
- the benzoic acid component, alcohol and phosphorus (I) compound at the beginning of step (A), to start heating and only then to at least some of the tin (II) oxide admit.
- the tin (II) oxide is preferably added before the reaction temperature of the reaction mixture is reached.
- the tin (II) oxide can be added if the temperature is between two thirds of the reaction temperature and the reaction temperature of the esterification.
- a suitable temperature range for the addition is, for example, between 150 and 190 ° C., in particular around 170 ° C.
- the mixture is then heated further to the esterification reaction temperature.
- step (A) is expediently continued until the residual content of the benzoic acid component in the reaction mixture has dropped to less than or equal to 5%. If benzoic acid itself is used as the benzoic acid component, the end time of the reaction after step (A) can also be determined on the basis of the acid number.
- the reaction in step (A) is expediently completed when the acid number is less than 25. This corresponds approximately to a residual acid content of 5% or less.
- the esterification is then continued after step (B), i.e. under reduced pressure.
- Step (B) serves to esterify the remaining amount of benzoic acid component.
- the pressure in the reaction vessel is expediently set such that at the selected reaction temperature Water or alcohol formed (methanol in the case of methyl benzoate as starting material) is distilled off from the reaction mixture in order to shift the reaction equilibrium to the side of the products.
- the vacuum should, if possible, not be so great that larger amounts of benzoic acid component are drawn off from the reaction mixture.
- a vacuum in the range of approximately 200 mbar has proven to be suitable.
- step (A) If only part of the tin (II) oxide was initially added in step (A), the remaining amount of this catalyst component is now added.
- the renewed addition of the tin oxide in step (B) is advantageous for as complete an esterification as possible.
- the reaction in step (B) is expediently continued until the residual content of the benzoic acid component in the reaction mixture has dropped to not more than 1%.
- step (C) the esterification reaction in a high vacuum is ended in step (C).
- the negative pressure in the reaction vessel is increased so much that water is virtually completely removed from the reaction mixture in the case of benzoic acid or lower alcohol in the case of a benzoic acid ester as a starting product.
- the esterification of the benzoic acid component is also completed, so that at the end of step (C) the acid number in the reactor is usually below 0.3 and the residual content of benzoic acid component in the reaction mixture has dropped to less than or equal to 0.1% , This means that the esterification reaction using the process according to the invention is practically complete and essentially without losses of benzoic acid component.
- step (C) of the esterification process according to the invention the reaction mixture is allowed to cool and the catalyst used according to the invention is precipitated.
- the addition of phosphoric acid is particularly suitable for this.
- the precipitated catalyst is then filtered off.
- the benzoic acid ester obtained is water-clear, has a very low acid number and a weak intrinsic odor. It can be used without further cleaning or preparation steps and can be used, for example, as received in preparations for cosmetic applications.
- the amount of catalyst used in the process according to the invention depends on the starting components used in the esterification. The optimum amount for the particular esterification reaction can easily be determined by a person skilled in the art.
- the amount of tin (II) oxide is between 0.01 and 0.6% by weight, in particular their 0.03 to 0.1 wt .-%, based on the benzoic acid component.
- the amount of phosphorus (I) compound is preferably between 0.02 and 1% by weight and in particular between 0.07 and 0.3% by weight, again based on the amount of benzoic acid component used.
- the tin (II) oxide can be added to the reaction mixture in several stages. It has proven advantageous to add a large part of the amount of tin oxide in step (A), amounts of between 60 and 95%, in particular between 75 and 90%, of the total amount of the tin oxide having proven to be expedient. The remaining amount is added in step (B).
- reaction temperatures also largely depend on the starting materials used.
- the reaction temperatures are generally between 150 and 290 ° C. A temperature range between 200 and 240 ° C. is particularly preferred.
- the temperature in steps (A), (B) and (C) differs from one another.
- the reaction temperature can be increased in the course of the esterification reaction in order to achieve the most complete possible reaction of the benzoic acid component with the alcohol.
- the esterification process according to the invention provides benzoic acid esters which can be used as basic substances in cosmetic preparations.
- alcohol and benzoic acid with 0.1% by weight of phosphoric (1) acid based on the amount of benzoic acid, are initially introduced at room temperature and under normal pressure.
- the reaction mixture is gradually heated with stirring.
- tin (II) oxide based on the amount of benzoic acid used, is added.
- the reaction mixture is further heated to a reaction temperature of 220 ° C. with stirring.
- the water formed during the esterification is distilled off from the reaction mixture.
- the reaction is continued at 220 ° C. under normal pressure until the residual acid content in the reaction mixture has dropped to below 5%.
- the acid number of the reaction mixture is less than 25.
- the esterification reaction is continued while maintaining the temperature of about 220 ° C. and applying a vacuum of about 200 mbar until a residual acid content of about 0.9% is reached in the reaction mixture.
- the vacuum is then increased to less than 10 mbar in order to separate unreacted alcohol from the reaction mixture.
- the acid number in the reactor drops to less than 0.3 and the residual acid content reaches a value of less than 0.065%.
- reaction mixture After the unreacted alcohol has been completely removed from the reaction mixture, the reaction mixture is allowed to cool to room temperature and phosphoric acid is added to precipitate the catalyst from the reaction mixture. The precipitated catalyst is separated off using a filter press.
- the benzoic acid ester obtained is dried in vacuo.
- the product is water-clear, has a low acid number and only a very weak smell. It is commercially available under the Cetiol ® AB brand from Cognis GmbH & Co. KG.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE10321107A DE10321107A1 (en) | 2003-05-09 | 2003-05-09 | Process for the preparation of a benzoic acid ester |
PCT/EP2004/004589 WO2004099117A1 (en) | 2003-05-09 | 2004-04-30 | Method for producing a benzoate |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1622859A1 true EP1622859A1 (en) | 2006-02-08 |
Family
ID=33394462
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04730508A Withdrawn EP1622859A1 (en) | 2003-05-09 | 2004-04-30 | Method for producing a benzoate |
Country Status (5)
Country | Link |
---|---|
US (1) | US20070185345A1 (en) |
EP (1) | EP1622859A1 (en) |
CN (1) | CN1784375A (en) |
DE (1) | DE10321107A1 (en) |
WO (1) | WO2004099117A1 (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20060058547A1 (en) * | 2004-09-07 | 2006-03-16 | Kao Corporation | Process for producing salicylic esters |
EP1905483A1 (en) * | 2006-09-27 | 2008-04-02 | Cognis IP Management GmbH | Alkyl benzoate mixtures |
TW201219353A (en) * | 2010-09-07 | 2012-05-16 | Daiichi Sankyo Co Ltd | Manufacturing method of benzoates |
CN112136810A (en) * | 2020-10-13 | 2020-12-29 | 江苏科技大学 | Methyl benzoate fumigant and application thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2182397A (en) * | 1937-07-09 | 1939-12-05 | Procter & Gamble | Manufacture of ether derivatives of polyhydric alcohols |
US3972962A (en) * | 1973-10-23 | 1976-08-03 | Emery Industries, Inc. | Non-migrating polymeric plasticizers for polyvinyl chloride |
US4275222A (en) * | 1978-10-10 | 1981-06-23 | Finetex, Inc. | Benzoate ester compositions |
US4548746A (en) * | 1984-05-14 | 1985-10-22 | Westvaco Corporation | Rosin pentaerythritol ester preparation improvement |
US4737569A (en) * | 1986-12-30 | 1988-04-12 | General Electric Company | Process for the production of substantially monoester-free diaryl esters of aromatic dicarboxylic acids |
US4791097A (en) * | 1987-03-09 | 1988-12-13 | Finetex, Inc. | Benzoic acid esters and their use |
US5006585A (en) * | 1989-09-05 | 1991-04-09 | Huls America Inc. | Stain-resistant plasticizer compositions and method of making same |
US5959130A (en) * | 1996-07-02 | 1999-09-28 | Finetex, Inc. | Castor based benzoate esters |
DE10110746A1 (en) * | 2001-03-07 | 2002-09-12 | Bayer Ag | Process for the preparation of benzyl hydroxybenzoates |
-
2003
- 2003-05-09 DE DE10321107A patent/DE10321107A1/en not_active Withdrawn
-
2004
- 2004-04-30 US US10/556,233 patent/US20070185345A1/en not_active Abandoned
- 2004-04-30 WO PCT/EP2004/004589 patent/WO2004099117A1/en active Application Filing
- 2004-04-30 CN CNA2004800126288A patent/CN1784375A/en active Pending
- 2004-04-30 EP EP04730508A patent/EP1622859A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO2004099117A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20070185345A1 (en) | 2007-08-09 |
DE10321107A1 (en) | 2004-11-25 |
WO2004099117A1 (en) | 2004-11-18 |
CN1784375A (en) | 2006-06-07 |
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Legal Events
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PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
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17P | Request for examination filed |
Effective date: 20051029 |
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AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): DE ES FR GB IT |
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DAX | Request for extension of the european patent (deleted) | ||
RBV | Designated contracting states (corrected) |
Designated state(s): DE ES FR GB IT |
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RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: KRUEPPEL, HEINZ-JOSEF Inventor name: FIEG, GEORG Inventor name: SUESSENBACH, ANDREAS Inventor name: SCHOLINAKIS, KONSTANTINOS Inventor name: SCHWERIN, ALBRECHT Inventor name: BIEHL, PETRA |
|
RIN1 | Information on inventor provided before grant (corrected) |
Inventor name: BIEHL, PETRA Inventor name: FIEG, GEORG Inventor name: KRUEPPEL, HEINZ-JOSEF Inventor name: SCHWERIN, ALBRECHT Inventor name: SCHOLINAKIS, KONSTANTINOS Inventor name: SUESSENBACH, ANDREAS |
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17Q | First examination report despatched |
Effective date: 20090330 |
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STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
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18D | Application deemed to be withdrawn |
Effective date: 20100310 |