CN103508881B - Alkyl salicylic acid synthesis method - Google Patents
Alkyl salicylic acid synthesis method Download PDFInfo
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- CN103508881B CN103508881B CN201210212044.1A CN201210212044A CN103508881B CN 103508881 B CN103508881 B CN 103508881B CN 201210212044 A CN201210212044 A CN 201210212044A CN 103508881 B CN103508881 B CN 103508881B
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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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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
Alkyl salicylate customary preparation methods is as follows: with phenol and alkene for raw material, obtain alkylphenol by alkylated reaction, is then made alkylphenol carboxylated by Kolbe-Schmitt reaction thus is provided alkyl salicylate.Patent EP370555, UK586461 all report and prepare alkyl salicylate by Kolbe-Schmitt flow process.In this flow process, Problems existing is: in the alkylphenol obtained after alkylation of phenol, there is chain alkyl and be positioned at ortho position and contraposition two kinds of situations, usual ratio is about 1:1, and ortho alkyl phenol activity is lower, be difficult to carboxylated in Kolbe-Schmitt reaction, thus only have an appointment in final alkylphenol total amount and 70% be usually converted into alkyl salicylate, this reduces directly causing raw material olefin utilization ratio, thus makes production cost high; Alkylphenol can not be converted into alkyl salicylate completely, in final product, therefore about has the free alkyl phenol of 30% to exist, product colour can be made excessively dark, had a strong impact on its application and sale.
A kind of method addressed this problem is by alkyl salicylate alkylation (such as: wintergreen oil), then makes the alkylated salicylamide acid alkyl ester of gained be hydrolyzed, to obtain alkyl salicylate.US5434293 discloses the method for alkylated salicylic acid alkyl ester.Should alkylated reaction transformation efficiency be higher in this way, but shortcoming be alkylated salicylamide acid alkyl ester can not complete hydrolysis, thus make product yield greatly reduce.
DD-A-269619 and DD-A-293108 reports alkene and alkylation of salicylic acid process, and the method requires that first the carboxyl in Whitfield's ointment and hydroxyl are separately converted to ester bond and ehter bond, then carries out alkylated reaction.The method synthesis technique is longer, requires that alkylating chain length is only below six carbon simultaneously.
Another simple method carrys out alkylated salicylic acid directly obtained alkyl salicylate with alkene.This preparation method has Patents report.Wherein CN1727323A to report with Whitfield's ointment and alkene as reactant, makes catalyzer to Whitfield's ointment direct alkylation with carried heteropoly acid.This invention adopts carried heteropoly acid as catalyzer, and introduce solvent, compared to general catalyzer, product and catalyzer are easy to be separated, and catalyzer can repeatedly use simultaneously.But during application the method synthesis of alkyl Whitfield's ointment, olefine reaction transformation efficiency is relatively low, and only up to 52.4%, therefore economy is poor.
US7045654 and CN1708470A discloses a kind of method preparing alkyl salicylate.This invention to relate to perfluoro alkyl sulfonic acid or alkylsulphonic acid as catalyzer, prepares alkylated salicylic acid by Whitfield's ointment and alhpa olefin.With respect to the product of Kolbe-Schmitt flow process synthesis gained, in the method synthetic product, alkylphenol content is very low, and product color 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 reclaimed after reaction in addition will inactivation, cannot recycle, because catalyzer price is high, thus 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 compared to current preparation method, and used catalyst is solid acid, to the corrosion-free effect of equipment, can recycle, and price is relatively low, effectively can reduces production cost.
Method provided by the invention comprises: the alkene being 4-50 carbon number mixes with Whitfield's ointment, at 50 DEG C-160 DEG C, alkylated reaction is carried out under the katalysis of aryl sulfonic acid, reaction times is 0.5-24 hour, Whitfield's ointment and alkene can 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, preferred 5-15%.
Temperature of reaction is 50 DEG C-160 DEG C.
Duration of the reaction is 0.5-24 hour, and the good reaction times is 4-10 hour.
The present invention relates to aryl sulfonic acid as catalyzer, compared to 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, be 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 four mouthfuls of round-bottomed flasks of 500ml that prolong is housed, add Whitfield's ointment 69.0g, adding n-butyl ether is 20ml, then adds 1-hexadecylene 112.2g, then adds the phospho-wolframic acid that 2.5g charge capacity is 20%.Pass into nitrogen, stir with magnetic stirring apparatus, temperature of reaction is 90 DEG C, 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 tetra-mouthfuls of round-bottomed flasks, add 1-hexadecylene 112.2g, stir with magnetic stirring apparatus, slowly add Whitfield's ointment 69.0g, then add 13.8g Phenylsulfonic acid.Pass into nitrogen, temperature of reaction is 120 DEG C, and the reaction times is 7 hours.After reaction terminates, add water and carry out washing to remove catalyzer, after stratification dewaters, obtain product alkyl salicylate.Olefine reaction transformation efficiency is 89.6%.
Embodiment 2
In 500ml tetra-mouthfuls of round-bottomed flasks, add 1-octadecylene 126.2g, stir with magnetic stirring apparatus, slowly add Whitfield's ointment 69.0g, then add 13.8g Phenylsulfonic acid.Pass into nitrogen, temperature of reaction is 130 DEG C, and the reaction times is 7 hours.After reaction terminates, add water and carry out washing to remove catalyzer, after stratification dewaters, obtain product alkyl salicylate.Olefine reaction transformation efficiency is 76.2%.
Embodiment 3
In 500ml tetra-mouthfuls of round-bottomed flasks, add C16C18 alkene 117.6g, stir with magnetic stirring apparatus, slowly add Whitfield's ointment 69.0g, then add 13.8g Phenylsulfonic acid.Pass into nitrogen, temperature of reaction is 130 DEG C, and the reaction times is 7 hours.After reaction terminates, add water and carry out washing to remove catalyzer, after stratification dewaters, obtain product alkyl salicylate.Olefine reaction transformation efficiency is 83.7%.
Claims (5)
1. the salicylic method of synthesis of alkyl, it is characterized in that: the method comprises: the alkene being 4-50 carbon number mixes with Whitfield's ointment, at 50 DEG C-160 DEG C, alkylated reaction is carried out under the katalysis of Phenylsulfonic acid, reaction times is 0.5-24 hour, Whitfield's ointment and alkene can in molar ratio between 1:0.8-1:2 arbitrary proportion add, the consumption of catalyzer Phenylsulfonic acid 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 consumption of catalyzer Phenylsulfonic acid is the 5-15% of Whitfield's ointment weight.
4. synthetic method according to claim 1, is characterized in that: the reaction times is 4-10 hour.
5. synthetic method according to claim 2, is characterized in that: said olefin carbon number is 10-20.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201210212044.1A CN103508881B (en) | 2012-06-21 | 2012-06-21 | Alkyl salicylic acid synthesis method |
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| CN201210212044.1A CN103508881B (en) | 2012-06-21 | 2012-06-21 | Alkyl salicylic acid synthesis method |
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| CN103508881A CN103508881A (en) | 2014-01-15 |
| CN103508881B true CN103508881B (en) | 2015-05-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019014255A1 (en) | 2017-07-11 | 2019-01-17 | Si Group, Inc. | Process for preparing alkyl salicylic acid and products thereof |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
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- 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019014255A1 (en) | 2017-07-11 | 2019-01-17 | Si Group, Inc. | Process for preparing alkyl salicylic acid and products thereof |
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