CN107459443A - A kind of preparation method of 2,6 di-t-butyl phenates - Google Patents
A kind of preparation method of 2,6 di-t-butyl phenates Download PDFInfo
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- CN107459443A CN107459443A CN201710874818.XA CN201710874818A CN107459443A CN 107459443 A CN107459443 A CN 107459443A CN 201710874818 A CN201710874818 A CN 201710874818A CN 107459443 A CN107459443 A CN 107459443A
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
- C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
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Abstract
The invention provides a kind of preparation method of 2,6 di-t-butyl phenates, in benzene kind solvent, under inert gas shielding, by 2,6 di-tert-butylphenols and alkali metal compound with 1:1~1:1.4 mol ratio reflux dewatering reacts 3 ~ 8h；Reaction cools under inert gas shielding after terminating, filtered, and vacuum drying, it is 2,6 di-t-butyl phenates to obtain off-white powder product.The present invention uses benzene kind solvent reflux dewatering, accelerates reaction process, shortens the reaction time, improves the combined coefficient of 2,6 di-t-butyl phenates；Benzene kind solvent can take away the impurity of unreacted raw material and generation in post-processing filtering, improve product purity；Obtained 2,6 di-t-butyl phenates colors are off-white color product, and quality is high, and purposes is wide；Inert gas shielding is used in reaction and last handling process, can effectively completely cut off air, reduce the production of accessory substance, improve the yield of 2,6 di-t-butyl phenates.
Description
Technical field
The present invention relates to the preparation method of one kind 2,6- di-t-butyl phenates, belong to compound synthesis technical field.
Background technology
2,6- di-t-butyl phenates are a kind of widely used antioxidants, are good catalyst, the nucleophilic of organic reaction
Reagent and organic alkali agents, it is widely used in the reaction such as nucleophilic displacement of fluorine, condensation.2,6- di-t-butyl phenates is also simultaneously
Important intermediate in organic synthesis, mainly for the manufacture of natural rubber and rubber polymer age resistor, plastic antioxidants, fuel stabilization
Agent, ultra-violet absorber and agricultural chemicals, dyestuff intermediate etc., principal item have antioxidant 1010, antioxidant 1076, antioxidant 612
Deng.
At present, oneself the disclosed report on 2,6- di-t-butyl phenates of warp mainly has four kinds of synthetic methods：
Firstth, using sodium alkoxide as alkali metal compound, in Organic Alcohol（Methanol, ethanol）Middle reaction, 2,6- di-t-butyl phenates is made；
Reaction time needed for this method is longer and obtained 2,6- di-t-butyls phenates color and luster is deeper, is unfavorable for the quality of subsequent product.
Secondth, under condition of no solvent, by 2,6- di-tert-butylphenols, alkali metal hydroxide（Sodium hydroxide, hydroxide
Potassium）It is heated to 180 ~ 250 DEG C of reactions and prepares 2,6- di-t-butyl phenates；Temperature needed for this method is high, and phenol easily distils, is not easy to grasp
Make.
3rd, solvent is done with water, alkali metal hydroxide（Sodium hydroxide, potassium hydroxide）Reacted with 2,6 phenol and prepare 2,6-
Di-t-butyl phenates；This method reaction yield is relatively low.
4th, the alkali metal such as metallic sodium, potassium directly reacts with 2,6- di-tert-butylphenols in organic solvent；This method uses
It is not easy to operate to alkali metal such as metallic sodium, potassium.
In addition, 2,6- di-t-butyl phenates are influenceed to be easy in preparation process by factors such as reaction temperature, solvents
It is oxidized, so also being had higher requirements for preparation process.
The content of the invention
For problem existing for prior art synthesis 2,6- di-t-butyl phenates, it is an object of the invention to provide one kind to react
The preparation method for the 2,6- di-t-butyl phenates that time is short, product purity is high, yield is high.
The present invention realizes that the technical scheme that above-mentioned purpose is taken is as follows：The preparation method of one kind 2,6- di-t-butyl phenates,
It is characterized in that：In benzene kind solvent, under inert gas shielding, by 2,6- di-tert-butylphenols and alkali metal compound with 1:1~1:
1.4 mol ratio reflux dewatering reacts 3 ~ 8h；Reaction cools under inert gas shielding after terminating, filtered, and vacuum drying, obtains
Off-white powder product is 2,6- di-t-butyl phenates.
The benzene kind solvent is one kind in benzene or toluene or dimethylbenzene, preferably toluene；The alkali metal compound is hydrogen
One kind in potassium oxide or sodium hydroxide or potassium tert-butoxide or sodium methoxide or caustic alcohol, preferably sodium hydroxide；Inert gas is nitrogen
Gas or argon gas, preferably argon gas.The dosage of benzene kind solvent is 3~6 times of 2,6- di-tert-butylphenol quality.
The present invention has advantages below compared with prior art：
1st, benzene kind solvent reflux dewatering is used in reacting, reaction process is accelerated, shortens the reaction time, improve the uncles of 2,6- bis-
The combined coefficient of butyl phenates；
2nd, benzene kind solvent can take away the impurity of unreacted raw material and generation in post-processing filtering, improve product purity；System
2, the 6- di-t-butyl phenates color obtained is off-white color, and quality is high, and purposes is wide；
3rd, inert gas shielding is used in reaction and last handling process, can effectively completely cuts off air, reduce the production of accessory substance,
Improve the yield of 2,6- di-t-butyl phenates.
Embodiment
The preparation method and yield of 2,6- di-t-butyls phenates of the present invention are carried out specifically below by specific experiment example
It is bright.
Embodiment 1；Accurately take 2,6- di-tert-butylphenols 41.2g（0.2mol）, sodium hydroxide 8.8g（0.22mol）With toluene
160g；Above-mentioned article addition frame is had in the three-necked flask of water knockout drum, replaces reaction flask 5min with argon gas, stirring is warming up to back
Stream, insulation reaction 6h；In the process, reaction solution is changed into white casse shape from colorless and transparent, has moisture to go out in water knockout drum, about
3.4ml；Reaction is filtered after terminating after water-bath under argon gas is protected is cooled to room temperature, vacuum drying, obtains off-white powder 41.5g,
As 2,6- di-t-butyl sodium phenolates, yield 91%.
Embodiment 2；Weigh 2,6- di-tert-butylphenols 41.2g (0.2mol), sodium hydroxide 9.6g（0.24mol）With toluene
240g；Above-mentioned article addition frame is had in the three-necked flask of water knockout drum, replaces reaction flask 5min with argon gas, stirring is warming up to back
Stream, insulation reaction 6h；In the process, reaction solution is changed into white casse shape from colorless and transparent, has moisture to go out in water knockout drum, about
3.4ml.Reaction is filtered after terminating after water-bath under argon gas is protected is cooled to room temperature, vacuum drying, obtains off-white powder 40.6g,
As 2,6- di-t-butyl sodium phenolates, yield 89%.
Embodiment 3；Weigh 2,6- di-tert-butylphenols 41.2g (0.2mol), sodium hydroxide 9.2g（0.24mol）With dimethylbenzene
200g, above-mentioned article addition frame is had in the three-necked flask of water knockout drum, replaces reaction flask 5min with argon gas, stirring is warming up to back
Stream, insulation reaction 5h；In the process, reaction solution is changed into white casse shape from colorless and transparent, has moisture to go out in water knockout drum, about
3.4ml.Reaction terminate after under nitrogen protection water-bath filtered after being cooled to room temperature, vacuum drying, obtain off-white powder 39.7g,
As 2,6- di-t-butyl sodium phenolates, yield 87%.
Embodiment 4；Weigh 2,6- di-tert-butylphenols 41.2g (0.2mol), potassium hydroxide 12.35g（0.22mol）With diformazan
Benzene 240g；Above-mentioned article addition frame is had in the three-necked flask of water knockout drum, replaces reaction flask 5min with argon gas, stirring is warming up to
Backflow, insulation reaction 5h；In the process, reaction solution is changed into white casse shape from colorless and transparent, has moisture to go out in water knockout drum,
About 3.4ml.Reaction terminate after under nitrogen protection water-bath filtered after being cooled to room temperature, vacuum drying, obtain off-white powder
43.2g, as 2,6- di-tert-butylphenol sylvite, yield 88.5%.
Embodiment 5；Weigh 2,6- di-tert-butylphenols 41.2g（0.2mol）, potassium hydroxide 13.5g（0.24mol）With toluene
200g；Above-mentioned article addition frame is had in the three-necked flask of water knockout drum, replaces reaction flask 5min with argon gas, stirring is warming up to back
Stream, insulation reaction 6h；In the process, reaction solution is changed into white casse shape from colorless and transparent, has moisture to go out in water knockout drum, about
3.4ml.Reaction terminate after under nitrogen protection water-bath filtered after being cooled to room temperature, vacuum drying, obtain off-white powder 41g, i.e.,
For 2,6- di-tert-butylphenol sylvite, yield 84%.
Embodiment 6；Weigh 2,6- di-tert-butylphenols 41.2g（0.2mol）, sodium methoxide 12.42g（0.23mol）With benzene
160g；Above-mentioned article is added in three-necked flask, replaces reaction flask 5min with argon gas, stirring is warming up to backflow, insulation reaction 6h；
In the process, reaction solution is changed into white casse shape from colorless and transparent.Reaction terminate after under nitrogen protection water-bath be cooled to
Filtered after room temperature, vacuum drying, obtain off-white powder 39.4g, as 2,6- di-t-butyl sodium phenolates, yield 86.5%.
Embodiment 7；Weigh 2,6- di-tert-butylphenols 41.2g (0.2mol), caustic alcohol 17.68g（0.26mol）With toluene
160g；Above-mentioned article is added in three-necked flask, with nitrogen displacement reaction flask 5min, stirring is warming up to backflow, insulation reaction
6h；In the process, reaction solution is changed into white casse shape from colorless and transparent.Water-bath cooling under nitrogen protection after reaction terminates
Filtered after to room temperature, vacuum drying, obtain off-white powder 38.12g, as 2,6- di-t-butyl sodium phenolates, yield 83.6%.
Embodiment 8；Weigh 2,6- di-tert-butylphenols 41.2g (0.2mol), potassium tert-butoxide 22.44g（0.24mol）With toluene
120g；Above-mentioned article is added in three-necked flask, with nitrogen displacement reaction flask 5min, stirring is warming up to backflow, insulation reaction
4h；In the process, reaction solution is changed into white casse shape from colorless and transparent.Water-bath cooling under nitrogen protection after reaction terminates
Filtered after to room temperature, vacuum drying, obtain off-white powder 40.02g, as 2,6- di-tert-butylphenol sylvite, yield 82%.
Embodiment 9；Weigh 2,6- di-tert-butylphenols 41.2g (0.2mol), sodium hydroxide 8.8g（0.22mol）With toluene
120g；Above-mentioned article addition frame is had in the three-necked flask of water knockout drum, with nitrogen displacement reaction flask 5min, stirring is warming up to back
Stream, insulation reaction 3h；In the process, reaction solution is changed into white casse shape from colorless and transparent, has moisture to go out in water knockout drum, about
3.0ml.Reaction terminate after under nitrogen protection water-bath filtered after being cooled to room temperature, vacuum drying, obtain off-white powder 35.57g,
As 2,6- di-t-butyl sodium phenolates, yield 78%.
Embodiment 10；Weigh 2,6- di-tert-butylphenols 41.2g (0.2mol), sodium hydroxide 8.8g（0.22mol）With toluene
120g；Above-mentioned article is added in three-necked flask, with nitrogen displacement reaction flask 5min, stirring is warming up to backflow, insulation reaction
8h；In the process, reaction solution is changed into white casse shape from colorless and transparent, has moisture to go out in water knockout drum, about 3.4ml.Reaction
Water-bath is filtered after being cooled to room temperature under nitrogen protection after end, vacuum drying, obtains off-white powder 39.9g, as 2,6- bis-
Tert-butyl phenol sodium salt, yield 87.5%.
Claims (6)
1. one kind 2, the preparation method of 6- di-t-butyl phenates, it is characterised in that：In benzene kind solvent, under inert gas shielding,
By 2,6- di-tert-butylphenols and alkali metal compound with 1:1~1:1.4 mol ratio reflux dewatering reacts 3 ~ 8h；After reaction terminates
Cool under inert gas shielding, filter, vacuum drying, it is 2,6- di-t-butyl phenates to obtain off-white powder product.
2. the preparation method of one kind 2,6- di-t-butyl phenates as claimed in claim 1, it is characterised in that：The benzene kind solvent is
Benzene or toluene or dimethylbenzene.
3. the preparation method of one kind 2,6- di-t-butyl phenates as claimed in claim 2, it is characterised in that：The dosage of benzene kind solvent
For 3~6 times of 2,6- di-tert-butylphenol quality.
4. the preparation method of one kind 2,6- di-t-butyl phenates as described in claim 1,2 or 3, it is characterised in that：The alkali gold
It is potassium hydroxide or sodium hydroxide or potassium tert-butoxide or sodium methoxide or caustic alcohol to belong to compound.
5. the preparation method of one kind 2,6- di-t-butyl phenates as claimed in claim 4, it is characterised in that：The inert gas is
Nitrogen or argon gas.
6. the preparation method of one kind 2,6- di-t-butyl phenates as claimed in claim 5, it is characterised in that：The benzene kind solvent is
Toluene, the alkali metal compound are sodium hydroxide, and the inert gas is argon gas.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109796331A (en) * | 2019-02-18 | 2019-05-24 | 甘肃省化工研究院有限责任公司 | A method of 3,5- di-tert-butyl-4-hydroxybenzoic acid is prepared with single solvent |
| CN110878009A (en) * | 2018-09-05 | 2020-03-13 | 万华化学集团股份有限公司 | Preparation method of bisphenol A salt |
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| US2903487A (en) * | 1955-09-23 | 1959-09-08 | Ethyl Corp | Metallic derivatives of hindered phenols |
| JPS63156746A (en) * | 1986-12-19 | 1988-06-29 | Mitsui Toatsu Chem Inc | Production of alkyl-substituted aromatic carboxylic acids |
| DE3390557C2 (en) * | 1983-12-01 | 1989-02-16 | Inst Khim Fiz An Sssr | Process for the preparation of beta- (4-hydroxy-3,5-di-tert-butylphenyl) -propionic acid alkyl esters |
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| 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 |
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|---|---|---|---|---|
| US2903487A (en) * | 1955-09-23 | 1959-09-08 | Ethyl Corp | Metallic derivatives of hindered phenols |
| DE3390557C2 (en) * | 1983-12-01 | 1989-02-16 | Inst Khim Fiz An Sssr | Process for the preparation of beta- (4-hydroxy-3,5-di-tert-butylphenyl) -propionic acid alkyl esters |
| JPS63156746A (en) * | 1986-12-19 | 1988-06-29 | Mitsui Toatsu Chem Inc | Production of alkyl-substituted aromatic carboxylic acids |
| CN1319584A (en) * | 2001-01-20 | 2001-10-31 | 湖北省化学研究所 | Process for preparing 3,5-di-tert-butyl salicylic acid |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110878009A (en) * | 2018-09-05 | 2020-03-13 | 万华化学集团股份有限公司 | Preparation method of bisphenol A salt |
| CN110878009B (en) * | 2018-09-05 | 2022-11-04 | 万华化学集团股份有限公司 | Preparation method of bisphenol A salt |
| CN109796331A (en) * | 2019-02-18 | 2019-05-24 | 甘肃省化工研究院有限责任公司 | A method of 3,5- di-tert-butyl-4-hydroxybenzoic acid is prepared with single solvent |
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