CN1319584A - Process for preparing 3,5-di-tert-butyl salicylic acid - Google Patents
Process for preparing 3,5-di-tert-butyl salicylic acid Download PDFInfo
- Publication number
- CN1319584A CN1319584A CN 01106441 CN01106441A CN1319584A CN 1319584 A CN1319584 A CN 1319584A CN 01106441 CN01106441 CN 01106441 CN 01106441 A CN01106441 A CN 01106441A CN 1319584 A CN1319584 A CN 1319584A
- Authority
- CN
- China
- Prior art keywords
- tert
- salicylic acid
- raw material
- water
- butyl salicylic
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
In preparation method of 3,5-di-tert-butyl salicylic acid 2,4-di-tert-butyl phenol is used as raw material, and through the following steps: dissolving raw material in low-grade alcohol whose weight is 1-5 times raw material, making the above-mentioned material react with alkali metal hydroxide whose weight is 0.8-1.2 times raw material for above 2 hr. at 50-80 deg.C, evaporating alcohol and water to obtain anhydrous 2,4-di-tert-butyl phenol salt, then making it react with CO2 gas for 2-5 hr. at 110-250 deg.c and 0.5-1.0 MPa to obtain 3,5-di-tert-butyl salicylate, dissolving said salicylate in water and using extracting agent to extract unreacted material, making liquid separation and drop-adding dilute acid in water-layer liquid to pH 2-3 to produce flocculate, filtering and drying, and subliming to obtain the invented pure product.
Description
The present invention relates to the preparation method of 3.5-di-t-butyl salicylic acid, particularly is the method for feedstock production 3.5-di-t-butyl salicylic acid with the 2.4-DI-tert-butylphenol compounds.
3.5-di-t-butyl bigcatkin willow
Produce medicine, agricultural chemicals, oxidation inhibitor, recording paper are with the synthesis material of chemical productss such as developer or the intermediate of product.Preparation 3.5-di-t-butyl salicylic acid has important goods to be worth.
3.5-a kind of method of di-t-butyl salicylic acid synthetic is to be raw material with the salicylic acid, react two trimethyl carbinols again, get 3.5-di-t-butyl salicylic acid, react four steps, productive rate is 51%, be easy to generate the aftertreatment trouble of by product, solvent, and environment is had pollution (referring to " Speciality Petrochemicals " 1988.6)
The clear 63-165341 of JP has reported that a kind of gas-liquid phase legal system is equipped with 3.5-di-t-butyl salicylic acid method, and this method is a raw material with the 2.4-DI-tert-butylphenol compounds, makes solvent with kerosene, in autoclave, carry out carboxylation reaction, synthetic 3.5-di-t-butyl salicylic acid, productive rate is 39%, there is a smell of gas for product.
The flat 2-290829 of JP has reported that gas-liquid phase legal system is equipped with 3.5-di-t-butyl salicylic acid method, this method is a raw material with the 2.4-DI-tert-butylphenol compounds, with ethylene glycol bisthioglycolate alkyl oxide etc. is solvent, in autoclave, carry out the synthetic 3.5-di-t-butyl salicylic acid of carboxylation reaction, productive rate 80%, this method aftertreatment complexity, cost is higher.
The flat 3-178947 of JP has introduced a kind of preparation method of 3.5-di-t-butyl salicylic acid, with the 2.4-DI-tert-butylphenol compounds is raw material, adopts the synthetic 3.5-di-t-butyl salicylic acid of negative pressure gas solid method, and productive rate is 87%, this method remains on negative pressure state in carboxylation reaction, operate more numerous.
The objective of the invention is to overcome the deficiency of above-mentioned synthetic 3.5-di-t-butyl salicylic acid, providing a kind of is raw material with the 2.4-DI-tert-butylphenol compounds, prepares the method for 3.5-di-t-butyl salicylic acid, this method productive rate height, cost is lower, the product purity height, and the solvent aftertreatment is easier to.
The technological line of realizing the object of the invention is that the 2.4-DI-tert-butylphenol compounds is dissolved in the lower alcohol solvent, adding alkali metal hydroxide again reacts, after reaction is finished, the Ex-all alcohol and water, obtain the 2.4-DI-tert-butylphenol compounds an alkali metal salt of solid state, carry out carboxylation reaction with carbon dioxide again, obtain 3.5-di-t-butyl salicylic acid.
3.5-the preparation method of di-t-butyl salicylic acid is a raw material with the 2.4-DI-tert-butylphenol compounds, its preparation process is as follows:
(1) the 2.4-DI-tert-butylphenol compounds is dissolved in the lower alcohol solvent, quantity of solvent is 1-5 a times of raw material weight, the alkali metal hydroxide that in described solvent, adds 0.8-1.2 times of mol of raw material mol amount again, (reaction is more than 2 hours at T50-80 ℃ to heat this mixture solution, steam the solvent alcohol and water then, get anhydrous 2.4-DI-tert-butylphenol compounds an alkali metal salt
(2) feed carbon dioxide in the product input autoclave with (1) and carry out carboxylation reaction, temperature of reaction T110-250 ℃, pressure 0.5-1.0Mpa, reaction times 2-5 hour, get 3.5-di-t-butyl salicylic acid an alkali metal salt,
(3) (2) products obtained therefrom is water-soluble, add extraction agent and extract unreacted raw material, and separatory,
(4) water layer of telling to (3) drips mass concentration 10-30% mineral acid to PH2-3, separates out water-fast floss, and filtration drying gets 3.5-di-t-butyl salicylic acid,
(5) with the 3.5-di-t-butyl salicylic acid of (4) at vacuum 0.085-0.099Mpa, distil under temperature T 80-200 ℃ pure 3.5-di-t-butyl salicylic acid product.
Described lower alcohol solvent is methyl alcohol, ethanol, propyl alcohol, Virahol, ethanol.
Described alkali metal hydroxide is potassium hydroxide, sodium hydroxide, lithium hydroxide solid or liquid.
Described mineral acid is hydrochloric acid, sulfuric acid or nitric acid.
3.5-the detection means of two uncles base salicylic acid: IR, X fluorescent, X ray, HPLC, NMR, every analytical procedure gets final product according to the test of instrument general operational requirement.
Effect of the present invention is that with the 2.4-DI-tert-butylphenol compounds be raw material, with the alkali metal hydroxide reaction, makes anhydrous powder shape 2.4 DI-tert-butylphenol compounds an alkali metal salts, uses CO then
2Gas carries out gas-solid phase carboxylation under middle pressure 0.5-1.0Mpa, synthetic 3.5-di-t-butyl salicylic acid, the transformation efficiency height, the aftertreatment of solvent is easier to, synthetic 3.5-di-t-butyl salicylic acid warp is in the 0.085-0.099Mpa vacuum, the product purity height of T80-200 ℃ of distillation is for Products Development such as medicine, agricultural chemicals provide the high-quality pure raw material.
Embodiment 1
Drop into the 200g2.4-DI-tert-butylphenol compounds in the 1000ml there-necked flask, 40g sodium hydroxide adds the 200g solvent methanol; after the stirring and dissolving; drop in the 1 liter autoclave, under nitrogen protection, heat, T50-70 ℃ the reaction 2 hours after; heat temperature raising steams the first alcohol and water under the normal pressure; first alcohol and water Ex-all after 50 minutes, the interior temperature of bottle this moment is raised to T110-200 ℃, gets the solid, powdery thing; after analyzing, confirm as 2.4-di-tert-butyl sodium phenolate, drop into then and feed CO in the still
2Gas is at pressure 0.5-1.0Mpa, temperature T 110-250 ℃ of following carboxylation reaction 2 hours, reaction is dissolved in water in still after finishing, vacuum is extracted its solution out, in solution, add the unreacted raw material of xylene extraction, behind the separatory, the sulfuric acid that drips mass concentration 10% under the agitation condition in the water layer of telling is arranged to PH2-3, separate out water-fast white floss, filter, warm water washing, drying make 3.5-di-t-butyl salicylic acid 201.6g, productive rate is 83.6%.This product vacuum 0.098Mpa, temperature T 80-200 ℃ of distillation purification down, is got snow-white 3.5-di-t-butyl salicylic acid 196.6g, sublimation rate 97.5%, fusing point is T162-164 ℃, HPLC purity is 98.5%.
Embodiment 2
In 1 liter autoclave, drop into the 210g2.4-DI-tert-butylphenol compounds, 41g potassium hydroxide, 200g methyl alcohol is warming up to 60 ℃ and starts stirring, reacts 2 hours, steams the mixture of first alcohol and water then under normal pressure.Under negative pressure 0.09Mpa, continue distillating carbinol and water, after sampling analysis is confirmed to obtain drying solid powdery 2.4-DI-tert-butylphenol compounds sylvite after 50 minutes, feed CO 140 ℃ of temperature T
2Gas, 1T110-250 ℃ of following carboxylation reaction 5 hours, temperature is chilled to below T90 ℃ then, add carboxylation product in the water 300ml dissolution kettle, take out solution in the still and add toluene 100ml, the extraction unreacted reactant, behind the separatory, under whipped state, drip mass concentration 20% hydrochloric acid in the water layer solution of telling to PH2-3, temperature of reaction T30 ℃, produce water insoluble floss 3.5-di-t-butyl salicylic acid, carry out suction filtration then, the Warm Wash filter cake, vacuum-drying gets 3.5-di-t-butyl salicylic acid 230.5g, productive rate 90.3%, fusing point are T162-163.5 ℃, and HPLC purity is 98.5%.
Embodiment 3
In 1 liter reactor, drop into 2.4-DI-tert-butylphenol compounds 100g, potassium hydroxide 31g, ethanol 500g is when being warmed up to T60 ℃, start stirring, reacted 2 hours down at T50-80 ℃, under normal pressure, distill out the second alcohol and water, and under negative pressure, continue distillation second alcohol and water, with the condenser overhead product that liquefies, to the distillation of T140 ℃ of temperature after 1 hour, get after the thing analysis confirmation obtains drying solid powdery 2.4-DI-tert-butylphenol compounds sylvite in the still, in still, feed CO
2Gas carries out carboxylation reaction, temperature of reaction T110-250 ℃, 2 hours reaction times, add the 200ml water dissolution, take out solution and add octane 200ml extraction unreacted reactant, behind the separatory, under agitation condition, in the water layer solution of telling, drip the nitric acid of mass concentration 10% to PH2-3, temperature of reaction T20-30 ℃, obtain white cotton-shaped 3.5-di-t-butyl salicylic acid, filter, the warm water washing leaching cake, a dry T80-200 ℃ distillation obtains 3.5-di-t-butyl salicylic acid 115g under vacuum 0.085-0.099Mpa, productive rate 90.1%, fusing point T161.5-163 ℃, HPLC purity 96%.
Embodiment 4
In 1 liter reactor, drop into 2.4-DI-tert-butylphenol compounds 100g; add lithium hydroxide 12g; butanols 200g; under nitrogen protection, be warmed up to T50 ℃, begin to stir, under normal pressure, distilled out the fourth alcohol and water 2 hours; liquefy with condenser; after 60 minutes, sampling analysis feeds CO after confirming to obtain drying solid powdery 2.4-DI-tert-butylphenol compounds lithium salts in still T140 ℃ of distillation
2Gas carried out carboxylation reaction 3 hours, temperature of reaction T110-250 ℃, reaction pressure 0.5-1.0Mpa, after having reacted, in still, add water 200ml dissolving, from still, take out solution, add heptane 150ml extraction unreacted reactant, behind the separatory, under whipped state, be added drop-wise to water layer solution to PH2-3 with mass concentration 10% hydrochloric acid, temperature of reaction T25-35 ℃, get water-fast floss, follow-up employing embodiment 3 same procedure are handled, obtain 3.5-di-t-butyl salicylic acid 105g, productive rate 85%, fusing point T161-163 ℃, HPLC purity 95%.
Embodiment 5
In 1 liter reactor, drop into 2.4-DI-tert-butylphenol compounds 100g, sodium hydroxide 24g; Virahol 200g; when being warmed up to T60 ℃ under the nitrogen protection; start stirring, reacted 2 hours down, distill out alcohol and water then at T55-80 ℃; with the condenser overhead product that liquefies; after T140 ℃ of temperature steamed 1 hour, get after the thing analysis confirmation obtains drying solid powdery 2.4-di-tert-butyl sodium phenolate in the still, in still, feed CO
2Gas carries out carboxylation reaction, temperature of reaction T110-250 ℃, 5 hours reaction times, be as cold as then below T90 ℃, add the 200ml water dissolution, take out solution and add sherwood oil 200ml extraction unreacted reactant, behind the separatory, the sulfuric acid that drips mass concentration 20% under agitation condition in the water layer solution of telling is to PH2-3, temperature of reaction T30 ℃, obtain cotton-shaped 3.5-two uncles base salicylic acid, filter, obtain 3.5-di-t-butyl salicylic acid 105g, productive rate 85% with the method drying of embodiment 3, fusing point T161-163 ℃, HPLC purity 95%.
Embodiment 6
In the autoclave of 1 liter, drop into the 2.4-DI-tert-butylphenol compounds of 100g, potassium hydroxide 23g, propyl alcohol 200g when being warmed up to T60 ℃, starts stirring, reacted 2 hours, under normal pressure, distill out third alcohol and water, with the condenser overhead product that liquefies, T140 ℃ of distillation after 1 hour, get after the thing analysis confirmation obtains drying solid powdery 2.4-DI-tert-butylphenol compounds sylvite in the still, in still, feed CO
2Gas carries out carboxylation reaction, and reaction conditions adds the 200ml water dissolution then with embodiment 3, take out solution and add hexane 200ml extraction unreacted reactant, the operation behind the separatory obtains 3.5-di-t-butyl salicylic acid 108g with embodiment 3, productive rate 87%, fusing point T161.5-163 ℃, HPLC purity 95%.
Embodiment 7
In 1 liter reactor, drop into 2.4-DI-tert-butylphenol compounds 100g, potassium hydroxide 30g ethanol 200g, operation with embodiment 3 makes 3.5-di-t-butyl salicylic acid sylvite then, add benzene 200ml extraction unreacted reactant after the water dissolution, behind the separatory, operation is with embodiment 3, get 3.5-di-t-butyl poplar acid 110g, productive rate 88%, fusing point T162-164 ℃, HPLC purity 97%.
Embodiment 8
In 1 liter reactor, drop into 2.4-DI-tert-butylphenol compounds 200g, potassium hydroxide 40g, propyl alcohol 200g, then, operate same embodiment (3), make the 3.5-di-tert-butyl salicylic acid sylvite aqueous solution, add ethylbenzene 100ml extraction unreacted reactant, behind the separatory, with embodiment 3 operate 3.5-di-tert-butyl salicylic acid 214g, productive rate: 86%, fusing point: T161.5-163.5 ℃, HPLC purity 96%.
Claims (5)
1. the preparation method of a 3.5-di-tert-butyl salicylic acid is a raw material with the 2.4-DI-tert-butylphenol compounds, and its feature and preparation process are as follows:
(1) the 2.4-DI-tert-butylphenol compounds is dissolved in the lower alcohol solvent, quantity of solvent is raw material weight 1-5 times, the alkali metal hydroxide that in described solvent, adds 0.8-1.2 times of mol of raw material mol amount again, heating this mixing solutions reacts more than 2 hours at T50-80 ℃, steam the solvent alcohol and water then, get anhydrous 2.4-DI-tert-butylphenol compounds an alkali metal salt
(2) feed carbon dioxide in the product input autoclave with (1) and carry out carboxylation reaction, temperature of reaction T110-250 ℃, pressure 0.5-1.0Mpa, reaction times 2-5 hour, get 3.5-di-t-butyl salicylic acid an alkali metal salt,
(3) (2) products obtained therefrom is soluble in water, add extraction agent and extract unreacted raw material, and separatory,
(4) drip mass concentration 10-30% mineral acid to PH2-3 in the water layer that (3) are told, separate out water-fast floss, filtration drying gets 3.5-di-t-butyl salicylic acid,
(5) with (4) 3.5-di-t-butyl salicylic acid at vacuum 0.085-0.099Mpa, temperature 80-200 ℃ (distil down pure 3.5-di-t-butyl salicylic acid product.
2. preparation method as claimed in claim 1 is characterized in that described lower alcohol is methyl alcohol, ethanol, propyl alcohol, Virahol, butanols.
3. preparation method as claimed in claim 1 is characterized in that described alkali metal hydroxide is potassium hydroxide, sodium hydroxide, lithium hydroxide.
4. preparation method as claimed in claim 1 is characterized in that described extraction agent is hexane, heptane, octane, sherwood oil, benzene,toluene,xylene, ethylbenzene.
5. preparation method as claimed in claim 1 is characterized in that described mineral acid is hydrochloric acid, sulfuric acid or nitric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011064412A CN1159283C (en) | 2001-01-20 | 2001-01-20 | Process for preparing 3,5-di-tert-butyl salicylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011064412A CN1159283C (en) | 2001-01-20 | 2001-01-20 | Process for preparing 3,5-di-tert-butyl salicylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1319584A true CN1319584A (en) | 2001-10-31 |
| CN1159283C CN1159283C (en) | 2004-07-28 |
Family
ID=4655454
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011064412A Expired - Lifetime CN1159283C (en) | 2001-01-20 | 2001-01-20 | Process for preparing 3,5-di-tert-butyl salicylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1159283C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412199C (en) * | 2006-04-29 | 2008-08-20 | 北京未名凯拓作物设计中心有限公司 | Method for increasing salicylic acid content in plant, and its special carrier |
| CN104086411A (en) * | 2014-07-18 | 2014-10-08 | 甘肃省化工研究院 | Method for synthesizing 3,5-di-tert-butyl-2-hydroxybenzoic acid |
| CN107459443A (en) * | 2017-09-25 | 2017-12-12 | 甘肃省化工研究院 | A kind of preparation method of 2,6 di-t-butyl phenates |
-
2001
- 2001-01-20 CN CNB011064412A patent/CN1159283C/en not_active Expired - Lifetime
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100412199C (en) * | 2006-04-29 | 2008-08-20 | 北京未名凯拓作物设计中心有限公司 | Method for increasing salicylic acid content in plant, and its special carrier |
| CN104086411A (en) * | 2014-07-18 | 2014-10-08 | 甘肃省化工研究院 | Method for synthesizing 3,5-di-tert-butyl-2-hydroxybenzoic acid |
| CN107459443A (en) * | 2017-09-25 | 2017-12-12 | 甘肃省化工研究院 | A kind of preparation method of 2,6 di-t-butyl phenates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1159283C (en) | 2004-07-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2274435A1 (en) | Recovery of organic acids | |
| CN111041203B (en) | Mixed extracting agent for nickel-lithium separation and separation method | |
| CN101157681A (en) | Method for preparing 1,3 propane sultone | |
| CN103012109B (en) | Preparation method of metal oleate | |
| CN100569724C (en) | A kind of preparation of alkyl aromatic aldehyde and separation method | |
| TW201217308A (en) | Process for producing a lactic acid-amine complex | |
| CN102897804A (en) | Method for preparing lithium carbonate directly from lithium chloride and carbon dioxide | |
| KR20150119141A (en) | Method for preparing methyl lactate | |
| CA2587802C (en) | Preparation of borohydride salts | |
| CN1319584A (en) | Process for preparing 3,5-di-tert-butyl salicylic acid | |
| CN106866393A (en) | A kind of preparation method of paradol | |
| CN1214002C (en) | Process for synthesizing hydrate of calcium phenolsulfonate | |
| CN108752217B (en) | Synthesis method of dolutegravir key intermediate 2, 4-difluorobenzylamine | |
| JPH07228590A (en) | Production of sucrose fatty acid ester | |
| CN111747985B (en) | Preparation and application of phenoxy dicarboxylic acid type functionalized ionic liquid | |
| CN105237340B (en) | Novel synthesis method for 4,4,4-trifluorobutanol | |
| CN109369346B (en) | Preparation method of pentafluorophenol | |
| CN102976901A (en) | Synthetic method for hybrid tertiary butyl phenol | |
| CN104812487B (en) | Ruthenium-based catalyst and its purposes in selective hydration aromatics or polyunsaturated compounds | |
| CN106243008B (en) | The preparation method of Vonoprazan fumarate intermediate 5- (2- fluorophenyls) -1H- pyrroles's -3- formaldehyde | |
| CN114560764B (en) | Method for preparing C22 tricarboxylic acid by directly maleylating linoleic acid | |
| CN111072455A (en) | Method for continuously preparing pentafluorophenol by microreactor | |
| CN107814687A (en) | A kind of synthetic method to chlorophenethylol | |
| CN1284759C (en) | Method for producing tetrahydro isomerized alpha acid | |
| CN115073268B (en) | 3, 3-trifluoropropanol and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: HUASHUO SCIENCE CO., LTD. Free format text: FORMER OWNER: HUBEI PROV. CHEMICAL RESEARCH INST. Effective date: 20090605 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20090605 Address after: No. 30 Guan Shan Road, Hongshan District, Hubei, Wuhan Patentee after: Huashuo Technology Co., Ltd. Address before: No. 30 Guan Shan Road, Hongshan District, Hubei, Wuhan Patentee before: Hubei Research Institute of Chemistry |
|
| CX01 | Expiry of patent term |
Granted publication date: 20040728 |
|
| CX01 | Expiry of patent term |