CN104447308B - The synthetic method of methyl hydroxybenzoate - Google Patents
The synthetic method of methyl hydroxybenzoate Download PDFInfo
- Publication number
- CN104447308B CN104447308B CN201410657755.9A CN201410657755A CN104447308B CN 104447308 B CN104447308 B CN 104447308B CN 201410657755 A CN201410657755 A CN 201410657755A CN 104447308 B CN104447308 B CN 104447308B
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- Prior art keywords
- methanol
- catalyst
- dehydrant
- reaction
- hydroxybenzoic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/49—Esterification or transesterification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the synthetic method of methyl hydroxybenzoate, add first in reaction vessel and under methanol, stirring, be slowly added into catalyst cation exchanger resin, add P-hydroxybenzoic acid, be warming up to backflow, after question response liquid is increased to uniform temperature, add dehydrant, second time adds methanol, continues stirring reaction, treats P-hydroxybenzoic acid reaction completely, terminate reaction, Filtration of catalyst and dehydrant, be distilled off the methanol of excess, separates out crystal.Beneficial effects of the present invention: (1) improve the productivity of methyl hydroxybenzoate under the common effect of catalyst and dehydrant；The most greatly shorten the generated time of methyl hydroxybenzoate, improve combined coefficient；(3) can significantly reduce the addition of catalyst, catalyst and dehydrant can be removed by filtering, greatly simplify last handling process, and catalyst is reusable through regeneration, has certain economic benefit.
Description
Technical field
The present invention relates to preservative preparing technical field, relate particularly to the synthetic method of methyl hydroxybenzoate.
Background technology
Nipagin ester i.e. p-Hydroxybenzoate is a class safely and effectively preservative used in the world, be widely used in food,
The industry such as cosmetics and medicine.Nipagin ester, sodium benzoate, potassium sorbate are international three big preservative, except Nipagin ester
Outward, other is all acid preservative, the antiseptic effect having had the most in acid condition, and Nipagin ester uses pH scope relatively
Extensively, having good antiseptic effect in the range of pH=3～8, it also has the features such as low toxicity, efficient, consumption is few simultaneously, is
One of food preservative that China gives priority to.Conventional has methyl hydroxybenzoate, ethyl ester, propyl ester.At present, in some American-European states
Family's methyl hydroxybenzoate is a kind of preservative that application is wide, has applied more in fields such as food, medicine, cosmetics.
Generally, the synthesis of methyl hydroxybenzoate is to be synthesized under sulphuric acid catalysis with P-hydroxybenzoic acid and excessive methanol.In a large number
Concentrated sulphuric acid need with dense NaOH, NaCO3Solution cyclic washing removes, and causes separating-purifying complexity, equipment corrosion serious.For
Solving this problem, numerous studies use solid acid, superpower solid acid, load acid to be catalyst.Although adopting of these catalyst
With solving the problems referred to above, no matter but use liquid acid or solid acid catalyst, all suffer from a problem: owing to methanol can not
Azeotrope with water, and the boiling point of methanol is relatively low, therefore, it is difficult to find suitable dehydrant, along with reaction is carried out, in reaction system
Water get more and more, the concentration making methanol and catalyst is more and more lower, and reaction is increasingly slower, therefore Metagin ester synthesis reaction
Time is longer, and productivity is difficult to improve.
Summary of the invention
The technical problem to be solved is to provide the synthetic method of a kind of methyl hydroxybenzoate for above-mentioned prior art, makes
Obtaining productivity to improve, shorten the response time, the cation exchange resin catalyst used simplifies last handling process, and capable of circulation
Use.
The present invention solves the synthetic method of the technical scheme is that methyl hydroxybenzoate of above-mentioned technical problem, in reaction vessel
Add first and under methanol, stirring, be slowly added into catalyst cation exchanger resin, add P-hydroxybenzoic acid, be warming up to
Backflow, after question response liquid is increased to uniform temperature, adds dehydrant, and second time adds methanol, continues stirring reaction,
Treat P-hydroxybenzoic acid reaction completely, terminate reaction, Filtration of catalyst and dehydrant, the methanol of excess is distilled off,
Separate out crystal.
By such scheme, add amount is methanol cumulative volume 1/2～the 2/3 of methanol first.
By such scheme, described P-hydroxybenzoic acid is calculated in molar ratio as 1:3～1:6, described catalysis with the consumption of methanol
It is the 5%～20% of P-hydroxybenzoic acid that agent cation exchange resin adds quality, and the addition quality of described dehydrant is to hydroxyl
Benzoic 13%～20%.
By such scheme, described dehydrant is 4A molecular sieve or 3A molecular sieve.
The present invention uses cation exchange resin to be catalyst, and adds dehydrant in building-up process, will reaction by dehydrant
Moisture in system constantly removes, and makes molecular balance constantly move to right, and beneficially methyl hydroxybenzoate productivity improves.And react the later stage
The concentration of methanol and catalyst does not almost change, and reaction rate is unaffected, shortens the response time.Catalyzing cation exchange resin
Agent simplifies last handling process, and can be recycled.Gained thick product proper amount of methanol recrystallization, and with activated carbon decolorizing, obtain
To methyl hydroxybenzoate fine work.
The method using the present invention, at feed molar ratio P-hydroxybenzoic acid: methanol=1:5 (mol ratio), catalyst charge is to hydroxyl
The 6.5% of yl benzoic acid, during response time 3.0h, P-hydroxybenzoic acid reaction is complete, and productivity reaches 80%, works as catalyst
Addition is the 13% of P-hydroxybenzoic acid, response time 3.0h, and productivity i.e. reaches 90%, the fusing point of products obtained therefrom at 126 DEG C～
Between 128 DEG C, consistent with document.
Beneficial effects of the present invention:
(1) under the common effect of catalyst and dehydrant, improve the productivity of methyl hydroxybenzoate；
(2) greatly shorten the generated time of methyl hydroxybenzoate of knowing clearly, improve combined coefficient；
(3) can significantly reduce the addition of catalyst, catalyst and dehydrant can be removed by filtering, greatly simplify post processing
Process, and catalyst is reusable through regeneration, has certain economic benefit.
Accompanying drawing explanation
Fig. 1 is the FTIR figure of sintetics of the present invention；
Fig. 2 is the standard IR spectrogram of methyl hydroxybenzoate.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be further described in detail, but this explanation will not be construed as limiting the invention.
Embodiment 1:
With 001 × 7Na type cation exchange resin as catalyst, with 4A molecular sieve as dehydrant, P-hydroxybenzoic acid and methanol
Carry out methyl hydroxybenzoate is synthesized.
Reaction rate of charge: methanol: P-hydroxybenzoic acid=5:1 (mol ratio), cation exchange resin is para hydroxybenzene
The 13% of formic acid quality, dehydrant is the 18% of P-hydroxybenzoic acid quality.
Cation exchange resin deionized water is soaked 24h, then soaks 24h with 5% hydrochloric acid solution, be washed till neutrality, sucking filtration,
Dry.
Equipped with agitator, reflux condensing tube, thermometer, constant pressure funnel reaction bulb in add about 1/2 methanol,
Being slowly added into cation exchange resin under stirring, add P-hydroxybenzoic acid, warm makes solid all dissolve, then heats up
To gentle reflux and keep.When question response temperature is increased to more than 80 DEG C, add partially dehydrated dose, continue stirring reaction,
And fast drop residue methanol, stir and continue to be heated to backflow, adding surplus when temperature is increased again to more than 80 DEG C
Remaining dehydrant, is kept stirring for backflow, and after about 3.0h, P-hydroxybenzoic acid reaction is completely, end reaction, filtered while hot,
Distillation filtrate, reclaims the methanol of excess.Separate out crystal, weigh.
Thick product is put in the round-bottomed flask with reflux condensing tube, adds appropriate methanol, be heated to reflux, make Metagin
Ester just dissolves.The micro-boiling of appropriate activated carbon is added for a moment, filtered while hot after the coldest.Filtrate crystallisation by cooling, sucking filtration.Washing,
Hang, dry, obtain methyl hydroxybenzoate fine work, weigh.
Embodiment 2:
With 001 × 7Na type cation exchange resin as catalyst, with 4A molecular sieve as dehydrant, P-hydroxybenzoic acid and methanol
Carry out methyl hydroxybenzoate is synthesized.
Reaction rate of charge: methanol: P-hydroxybenzoic acid=5:1 (mol ratio), cation exchange resin is para hydroxybenzene first
The 6.5% of acid quality, dehydrant is the 18% of P-hydroxybenzoic acid quality.
Cation exchange resin deionized water is soaked 24h, then soaks 24h with 5% hydrochloric acid solution, be washed till neutrality, sucking filtration,
Dry.
Equipped with agitator, reflux condensing tube, thermometer, constant pressure funnel reaction bulb in add about 1/2 methanol,
Being slowly added into ion exchange resin under stirring, add P-hydroxybenzoic acid, warm makes solid all dissolve, then is warming up to
Gentle reflux also keeps.When question response temperature is increased to more than 80 DEG C, add partially dehydrated dose, continue stirring reaction, and
Fast drop residue methanol, stirs and continues to be heated to backflow, adding residue when temperature is increased again to more than 80 DEG C
Dehydrant, be kept stirring for backflow, after about 3.0h, P-hydroxybenzoic acid reaction is completely, terminates reaction, filtered while hot, steams
Evaporate filtrate, reclaim the methanol of excess.Separate out crystal, weigh.
Thick product is put in the round-bottomed flask with reflux condensing tube, adds appropriate methanol, be heated to reflux, make methyl hydroxybenzoate
Just dissolve.The micro-boiling of appropriate activated carbon is added for a moment, filtered while hot after the coldest.Filtrate crystallisation by cooling, sucking filtration.Washing, dries in the air
Put, dry, obtain methyl hydroxybenzoate fine work, weigh.
Embodiment 3:
With D72 type cation exchange resin as catalyst, with 4A molecular sieve as dehydrant, P-hydroxybenzoic acid and methanol are carried out
Methyl hydroxybenzoate is synthesized.
Reaction rate of charge: methanol: P-hydroxybenzoic acid=4:1 (mol ratio), cation exchange resin is para hydroxybenzene first
The 13% of acid quality, dehydrant is the 15% of P-hydroxybenzoic acid quality.
Cation exchange resin deionized water is soaked 24h, then soaks 24h with 5% hydrochloric acid solution, be washed till neutrality, sucking filtration,
Dry.
Equipped with agitator, reflux condensing tube, thermometer, constant pressure funnel reaction bulb in add 1/2 methanol,
Being slowly added into ion exchange resin under stirring, add P-hydroxybenzoic acid, warm makes solid all dissolve, then is warming up to
Gentle reflux also keeps.When question response temperature is increased to more than 80 DEG C, add partially dehydrated dose, continue stirring reaction, and
Fast drop residue methanol, stirs and continues to be heated to backflow, adding residue when temperature is increased again to more than 80 DEG C
Dehydrant, be kept stirring for backflow, after about 3.0h, P-hydroxybenzoic acid reaction is completely, terminates reaction, filtered while hot, steams
Evaporate filtrate, reclaim the methanol of excess.Separate out crystal, weigh.
Thick product is put in the round-bottomed flask with reflux condensing tube, adds appropriate methanol, be heated to reflux, make Metagin
Ester just dissolves.The micro-boiling of appropriate activated carbon is added for a moment, filtered while hot after the coldest.Filtrate crystallisation by cooling, sucking filtration.Washing,
Hang, dry, obtain methyl hydroxybenzoate fine work, weigh.
Fig. 1 is the FTIR figure of repeatedly recrystallization product.3300cm in figure-1-OH the absworption peak at place, 1680cm-1The C=O at place inhales
Receive peak, be phenyl ring absworption peak at 1590,1510, C-O absworption peak at 1290, phenyl ring in the range of 1000-600 in finger print region
The out-of-plane bending vibration absworption peak of upper c h bond all shows that this synthetic is methyl hydroxybenzoate.Fig. 2 is the mark of methyl hydroxybenzoate
Quasi-spectrogram.Contrasting visible, the spectrogram of the two is similar.Illustrate that synthetic product is really for methyl hydroxybenzoate.
Claims (1)
1. the synthetic method of methyl hydroxybenzoate, it is characterised in that add methanol in reaction vessel first, add methanol first
Amount is the 1/2～2/3 of methanol cumulative volume, is slowly added into catalyst cation exchanger resin, adds para hydroxybenzene first under stirring
Acid, is warming up to backflow, when question response liquid is increased to more than 80 DEG C, adds dehydrant, and described dehydrant is 4A molecule
Sieve or 3A molecular sieve, second time adds methanol, continues stirring reaction, treats P-hydroxybenzoic acid reaction completely, terminates reaction,
Filtration of catalyst and dehydrant, be distilled off the methanol of excess, separates out crystal；Described P-hydroxybenzoic acid and methanol
Consumption is calculated in molar ratio as 1:3～1:6, and it is P-hydroxybenzoic acid that described catalyst cation exchanger resin adds quality
5%～20%, addition quality is P-hydroxybenzoic acid 13%～the 20% of described dehydrant.
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| CN201410657755.9A CN104447308B (en) | 2014-11-18 | 2014-11-18 | The synthetic method of methyl hydroxybenzoate |
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| CN201410657755.9A CN104447308B (en) | 2014-11-18 | 2014-11-18 | The synthetic method of methyl hydroxybenzoate |
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| CN104447308A CN104447308A (en) | 2015-03-25 |
| CN104447308B true CN104447308B (en) | 2016-09-21 |
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| CN109879753A (en) * | 2019-03-05 | 2019-06-14 | 陕西科技大学 | A method of preparing paraben esters |
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| CN102921363A (en) * | 2012-11-02 | 2013-02-13 | 常州大学 | Method and device for removing water in microwave airtight reactor |
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| CN101759566A (en) * | 2008-11-19 | 2010-06-30 | 孟奇伟 | Method for catalyzing and synthesizing butylparaben by using gallium sulfate |
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| CN102921363A (en) * | 2012-11-02 | 2013-02-13 | 常州大学 | Method and device for removing water in microwave airtight reactor |
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Inventor after: Liu Yaqun Inventor after: Chen Wenjun Inventor after: Chen Yanwu Inventor before: Liu Yaqun Inventor before: Chen Yanwu |
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