CN103508881A - Alkyl salicylic acid synthesis method - Google Patents
Alkyl salicylic acid synthesis method Download PDFInfo
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- CN103508881A CN103508881A CN201210212044.1A CN201210212044A CN103508881A CN 103508881 A CN103508881 A CN 103508881A CN 201210212044 A CN201210212044 A CN 201210212044A CN 103508881 A CN103508881 A CN 103508881A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract
The present invention discloses an alkyl salicylic acid synthesis method, which comprises: mixing olefin with a carbon number of 4-50 and salicylic acid, and carrying out an alkylation reaction under a catalysis effect of aryl sulfonic acid at a temperature of 50-160 DEG C. According to the present invention, aryl sulfonic acid is adopted as a catalyst, a conversion rate can achieve 60-95%, the catalyst does not cause corrosion on the equipment, price is relatively low, the catalyst can be recycled, no three-waste emission problem exists, and environmental protection is easily achieved.
Description
(1) technical field
The present invention relates to a kind of salicylic method of synthesis of alkyl.
(2) background technology
Conventional preparation method is as follows for alkyl salicylate: take phenol and alkene as raw material, by alkylated reaction, make alkylphenol, thereby then by Kolbe-Schmitt, reacted the carboxylated alkyl salicylate that provides of alkylphenol is provided.Patent EP370555, UK586461 have all reported by Kolbe-Schmitt flow process and have prepared alkyl salicylate.The problem existing in this flow process is: in the alkylphenol obtaining after alkylation of phenol, exist chain alkyl to be positioned at ortho position and two kinds of situations of contraposition, conventionally ratio is about 1:1, and ortho position alkylphenol activity is lower, in Kolbe-Schmitt reaction, be difficult to by carboxylated, thereby in final alkylphenol total amount, only have an appointment and 70% be conventionally converted into alkyl salicylate, this will directly cause raw material olefin utilization ratio to reduce, thereby make production cost high; Alkylphenol can not be converted into alkyl salicylate completely, therefore in final product, approximately has 30% free alkyl phenol existence, can make product colour excessively dark, has had a strong impact on its application and sale.
A kind of method addressing this problem by alkyl salicylate alkylation (for example: wintergreen oil), then make the alkylated salicylamide acid alkyl ester hydrolysis of gained, to obtain alkyl salicylate is.US5434293 discloses the method for alkylation alkyl salicylate.Alkylated reaction transformation efficiency is higher in this way, but shortcoming be alkylated salicylamide acid alkyl ester can not complete hydrolysis, thereby product yield is reduced greatly.
DD-A-269619 and DD-A-293108 have reported alkene and alkylation of salicylic acid process, and the method requires carboxyl and the hydroxyl in Whitfield's ointment to be first separately converted to ester bond and ehter bond, then carries out alkylated reaction.The method synthesis technique is longer, and require alkylating chain length is only six below carbon simultaneously.
Another simple method is to come alkylation Whitfield's ointment directly to make alkyl salicylate with alkene.The existing Patents report of this preparation method.Wherein CN1727323A has reported that take Whitfield's ointment and alkene is reactant, makes catalyzer to Whitfield's ointment direct alkylation with carried heteropoly acid.This invention adopts carried heteropoly acid as catalyzer, introduces solvent simultaneously, and than general catalyzer, it is separated that product and catalyzer are easy to, and catalyzer can repeatedly be used.But during application the method synthesis of alkyl Whitfield's ointment, olefine reaction transformation efficiency is relatively low, and only up to 52.4%, so economy is poor.
US7045654 and CN1708470A disclose a kind of method of preparing alkyl salicylate.This invention relates to perfluoro alkyl sulfonic acid or alkylsulphonic acid as catalyzer, by Whitfield's ointment and alhpa olefin, prepares alkylation Whitfield's ointment.With respect to synthesize the product of gained by Kolbe-Schmitt flow process, in the method synthetic product, alkylphenol content is very low, and product color and luster is fabulous.But the defect of the method is: catalyzer alkylsulphonic acid is mostly liquid acid, has severe corrosive, higher to equipment requirements, the catalyzer reclaiming after reaction in addition will inactivation, cannot recycle, because catalyzer price is high, thereby be difficult to realize scale operation.
Above-mentioned disclosure is introduced in full as a reference at this.
(3) summary of the invention
The invention provides a kind of salicylic method of synthesis of alkyl.
The object of the invention is to provide a kind of synthesis of alkyl salicylic method, the method is than current preparation method, and used catalyst is solid acid, to the corrosion-free effect of equipment, can recycle, and price is relatively low, can effectively reduce production costs.
Method provided by the invention comprises: the alkene that is 4-50 carbon number mixes with Whitfield's ointment, under the katalysis of aryl sulfonic acid, at 50 ℃-160 ℃, carry out alkylated reaction, reaction times is 0.5-24 hour, Whitfield's ointment and alkene in molar ratio between 1:0.8-1:2 arbitrary proportion add, the consumption of catalyzer is the 2-60% of Whitfield's ointment weight.
Said olefin carbon number is 4-50, more preferably 8-40, and best scope is 10-20.
Said catalyzer is aryl sulfonic acid, and preferably the aryl of this sulfonic acid has an about 6-30 carbon atom, more preferably Phenylsulfonic acid.The consumption of catalyzer is the 2-60% of Whitfield's ointment weight, preferably 5-15%.
Temperature of reaction is 50 ℃-160 ℃.
Duration of the reaction is 0.5-24 hour, and the reaction times is 4-10 hour preferably.
The present invention relates to aryl sulfonic acid as catalyzer, than general catalyzer, this catalyzer has stronger acidity, reaction conversion ratio can reach 60%-95%, and catalyzer is to the corrosion-free effect of equipment, price is relatively low, can repeatedly recycle, and three-waste free discharge problem, is conducive to environmental protection.
Accompanying drawing explanation
Fig. 1 is the salicylic mass spectrum of 16 thiazolinyl that embodiment 1 obtains.
Fig. 2 is the salicylic mass spectrum of 18 thiazolinyl that embodiment 2 obtains.
Fig. 3 is the salicylic mass spectrum of 16,18 mixing thiazolinyl that embodiment 3 obtains.
Below in conjunction with embodiment, the present invention is described in detail.
(4) embodiment
Comparative example 1
In the four-hole round-bottomed flask of 500ml that prolong is housed, add Whitfield's ointment 69.0g, adding n-butyl ether is 20ml, then adds 1-hexadecylene 112.2g, and then adding 2.5g charge capacity is 20% phospho-wolframic acid.Pass into nitrogen, with magnetic stirring apparatus, stir, temperature of reaction is 90 ℃, and the reaction times is 3 hours.Then layered filtration, carries out vacuum distilling, finally obtains the finished product.Olefine reaction transformation efficiency is 42.0%.
Embodiment 1
In 500ml four-hole round-bottomed flask, add 1-hexadecylene 112.2g, with magnetic stirring apparatus, stir, slowly add Whitfield's ointment 69.0g, then add 13.8g Phenylsulfonic acid.Pass into nitrogen, temperature of reaction is 120 ℃, and the reaction times is 7 hours.After reaction finishes, add water and wash to remove catalyzer, after stratification dewaters, obtain product alkyl salicylate.Olefine reaction transformation efficiency is 89.6%.
In 500ml four-hole round-bottomed flask, add 1-octadecylene 126.2g, with magnetic stirring apparatus, stir, slowly add Whitfield's ointment 69.0g, then add 13.8g Phenylsulfonic acid.Pass into nitrogen, temperature of reaction is 130 ℃, and the reaction times is 7 hours.After reaction finishes, add water and wash to remove catalyzer, after stratification dewaters, obtain product alkyl salicylate.Olefine reaction transformation efficiency is 76.2%.
Embodiment 3
In 500ml four-hole round-bottomed flask, add C16C18 alkene 117.6g, with magnetic stirring apparatus, stir, slowly add Whitfield's ointment 69.0g, then add 13.8g Phenylsulfonic acid.Pass into nitrogen, temperature of reaction is 130 ℃, and the reaction times is 7 hours.After reaction finishes, add water and wash to remove catalyzer, after stratification dewaters, obtain product alkyl salicylate.Olefine reaction transformation efficiency is 83.7%.
Claims (7)
1. the salicylic method of synthesis of alkyl, it is characterized in that: the method comprises: the alkene that is 4-50 carbon number mixes with Whitfield's ointment, under the katalysis of aryl sulfonic acid, at 50 ℃-160 ℃, carry out alkylated reaction, reaction times is 0.5-24 hour, Whitfield's ointment and alkene in molar ratio between 1:0.8-1:2 arbitrary proportion add, the consumption of catalyzer is the 2-60% of Whitfield's ointment weight.
2. synthetic method according to claim 1, is characterized in that: said olefin carbon number is 8-40.
3. synthetic method according to claim 1, is characterized in that: the aryl of said aryl sulfonic acid has 6-30 carbon atom.
4. synthetic method according to claim 1, is characterized in that: the consumption of catalyzer is the 5-15% of Whitfield's ointment weight.
5. synthetic method according to claim 1, is characterized in that: the reaction times is 4-10 hour.
6. synthetic method according to claim 2, is characterized in that: said olefin carbon number is 10-20.
7. synthetic method according to claim 3, is characterized in that: said catalyzer is Phenylsulfonic acid.
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| CN201210212044.1A CN103508881B (en) | 2012-06-21 | 2012-06-21 | Alkyl salicylic acid synthesis method |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777537A (en) * | 2014-12-23 | 2016-07-20 | 中国石油天然气股份有限公司 | Alkylation method for salicylic acid |
| CN106316838A (en) * | 2015-07-09 | 2017-01-11 | 中国石油天然气股份有限公司 | Alkyl 2-hydroxy-3-naphthoic acid and preparation method thereof |
| CN107986961A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | The preparation method of alkyl salicylate and/or alkyl salicylate |
| WO2019014255A1 (en) * | 2017-07-11 | 2019-01-17 | Si Group, Inc. | Process for preparing alkyl salicylic acid and products thereof |
| CN111170850A (en) * | 2019-12-26 | 2020-05-19 | 山东源根石油化工有限公司 | Additive, preparation method and lubricating oil using additive |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415792A (en) * | 1993-12-23 | 1995-05-16 | Chevron Chemical Company | Overbased alkylated alkyl salicylates |
| CN1203572A (en) * | 1995-10-31 | 1998-12-30 | 罗狄亚化学公司 | Method for c-alkylating hydroxylated aromatic compounds |
| CN1708470A (en) * | 2002-10-31 | 2005-12-14 | 克鲁普顿公司 | Method for the alkylation of salicylic acid |
-
2012
- 2012-06-21 CN CN201210212044.1A patent/CN103508881B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5415792A (en) * | 1993-12-23 | 1995-05-16 | Chevron Chemical Company | Overbased alkylated alkyl salicylates |
| CN1203572A (en) * | 1995-10-31 | 1998-12-30 | 罗狄亚化学公司 | Method for c-alkylating hydroxylated aromatic compounds |
| CN1708470A (en) * | 2002-10-31 | 2005-12-14 | 克鲁普顿公司 | Method for the alkylation of salicylic acid |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105777537A (en) * | 2014-12-23 | 2016-07-20 | 中国石油天然气股份有限公司 | Alkylation method for salicylic acid |
| CN105777537B (en) * | 2014-12-23 | 2018-04-03 | 中国石油天然气股份有限公司 | A kind of alkylation of salicylic acid method |
| CN106316838A (en) * | 2015-07-09 | 2017-01-11 | 中国石油天然气股份有限公司 | Alkyl 2-hydroxy-3-naphthoic acid and preparation method thereof |
| CN106316838B (en) * | 2015-07-09 | 2020-02-14 | 中国石油天然气股份有限公司 | Alkyl 2-hydroxy-3-naphthoic acid and preparation method thereof |
| CN107986961A (en) * | 2016-10-26 | 2018-05-04 | 中国石油化工股份有限公司 | The preparation method of alkyl salicylate and/or alkyl salicylate |
| CN107986961B (en) * | 2016-10-26 | 2020-08-18 | 中国石油化工股份有限公司 | Process for preparing alkyl salicylic acid and/or alkyl salicylate |
| WO2019014255A1 (en) * | 2017-07-11 | 2019-01-17 | Si Group, Inc. | Process for preparing alkyl salicylic acid and products thereof |
| CN111170850A (en) * | 2019-12-26 | 2020-05-19 | 山东源根石油化工有限公司 | Additive, preparation method and lubricating oil using additive |
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