Method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids

A technology of acidic ionic liquid and n-butyl salicylate, which is applied in the field of esterification reaction and acidic ionic liquid of bis-secondary amine salts, can solve the problems of small market supply and high price of imidazole, and solve the problems of recycling, catalysts, etc. The effect of low dosage and high purity

Inactive Publication Date: 2014-06-25
CHANGZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But the price of imidazole is quite expensive, there is no large-scale industrial production at present, and the market supply is very small. Therefore, it is important to find and research the precursors that are relatively cheap and have more unique physical and chemical prope

Method used

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  • Method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids
  • Method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids
  • Method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] When HY acid is sulfuric acid.

[0031] Add 7.10ml of 1,4-dibromobutane into a 250ml three-neck flask with a mechanical stirring device, add 80ml of acetonitrile as a solvent, and add 15.06ml of homopiperidine dropwise to 1,4-dibromobutane in an ice-water bath at 0°C Stir vigorously in the bromobutane solution at the same time, reflux in a water bath at 70°C under nitrogen protection for 24h; filter the obtained solid, wash with acetone 3 times and filter again, then dry at 1.33Pa at 70°C for 5h to obtain milky white needle-like crystals, which are bis-secondary amine salts. Then take 3.9g of bis-secondary amine salt and add it to a 250ml three-necked flask, add 80ml of dichloromethane to make it fully dissolved, then slowly add 1ml of 97% sulfuric acid according to the ratio of the amount of substances to 1:2, blow nitrogen, and reflux in a water bath at 40°C After 48 hours, dichloromethane was removed by rotary evaporation, washed twice with anhydrous ether and then r...

Embodiment 2

[0033] When the HY acid is p-benzenesulfonic acid.

[0034] Add 7.10ml of 1,4-dibromobutane into a 250ml three-necked flask with a mechanical stirring device, add 80ml of acetonitrile as a solvent, and add 15.06ml of homopiperidine dropwise to 1,4- Stir vigorously in the dibromobutane solution at the same time, reflux in a water bath at 70°C under nitrogen protection for 2 hours; filter the obtained solid, wash with acetone 5 times and filter again, then dry at 1.33Pa at 50°C for 8 hours to obtain milky white needle-like crystals, which are bis-secondary amine salts . Then take 3.9g of bis-secondary amine salt and add it to a 250ml three-neck flask, add 80ml of dichloromethane to make it fully dissolved, then slowly add p-toluenesulfonic acid according to the ratio of the substance to 1:2, blow nitrogen, and reflux in a water bath at 20°C for 5h , rotary evaporated to remove dichloromethane, washed twice with anhydrous ether and rotary evaporated again, then dried at 50°C for...

Embodiment 3

[0036] Use the ionic liquid in embodiment 1 as catalyst

[0037]In a 250ml three-neck flask equipped with a water separator, an electric stirrer and a thermometer, react salicylic acid and n-butanol at a molar ratio of 1:1, and feed in a molar ratio of 1:1.5, and excess n-butanol is used as a water-carrying agent , Weigh 13.83g of salicylic acid and 13.73ml of n-butanol, first add the weighed salicylic acid and n-butanol into the three-necked flask, heat and stir at low temperature, and add 0.2766g of salicylic acid when it is completely dissolved The ionic liquid bis-(1-homopiperidine)butylene hydrogensulfate was used as a catalyst, and the addition amount was 2% of the mass of salicylic acid, and then the temperature was raised to 110°C, and the temperature was refluxed for 4 hours, and the water was divided in time during the reaction process. The conversion rate of salicylic acid can reach 94.38%, and the selectivity of n-butyl salicylate is 95.14%.

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Abstract

The technical scheme adopted by the invention is as follows: the invention discloses a method for catalyzed synthesis of n-butyl salicylate and tributyl citrate by di-sec-butylamine acidic ionic liquids, and a structural formula of the ionic liquids is as shown in the specification, wherein Y is hydrogen sulfate radical or p-toluenesulfonic acid radical. The invention develops novel varieties of acidic ion liquids, wherein the novel acidic ion liquids are dual-core high-piperidine structures which are very stable; thermal decomposition points of two ionic liquids according to a thermogravimetric analysis test are over 340 DEG C; the stability of the novel two ionic liquids is higher than that of most of ionic liquids; the two ionic liquids have stronger acidity, and the PH values are stronger than that of sulfuric acid under the same concentration. According to the invention, two ionic liquids are developed and utilized as acidic catalysts for respectively synthesizing n-butyl salicylate and tributyl citrate in a catalytic manner, so that the conversion rate of about 96% can be obtained, and ionic liquids can be recycled; compared with the normal method, the conversation rate of the n-butyl salicylate in the method disclosed by the invention is greatly improved.

Description

technical field [0001] The invention belongs to the application field of ionic liquids, in particular to a bis-secondary amine salt acidic ionic liquid used for esterification. Background technique [0002] N-butyl salicylate is an edible spice prescribed by my country. It is a widely used organic chemical raw material with a clear fragrance. It is currently widely used in the fields of daily chemicals and food additives. [0003] Tributyl citrate (TBC) is a non-toxic plasticizer approved by the U.S. Food and Drug Administration (FDA). It has the advantages of good compatibility, high plasticizing efficiency, non-toxicity, and low volatility. It does not grow mold, has mildew resistance, and has a wide range of uses. [0004] The traditional method of synthesizing n-butyl salicylate and TBC is mainly concentrated sulfuric acid catalytic esterification. However, this process has disadvantages such as many side reactions, dark product color, complex post-treatment process, s...

Claims

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Application Information

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IPC IPC(8): C07C69/84C07C69/704C07C67/08B01J31/02
CPCB01J31/0282B01J2231/49C07C67/08C07D223/04C07C69/84C07C69/704
Inventor 李工郭剑桥
Owner CHANGZHOU UNIV
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