CN102838482B - Preparation method of 3,6-dichlorosalicylic acid - Google Patents
Preparation method of 3,6-dichlorosalicylic acid Download PDFInfo
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Abstract
The invention discloses a preparation method of 3,6-dichlorosalicylic acid, which comprises the following steps: reacting 2,5-dichlorophenol and inorganic alkali to generate 2,5-dichlorophenate; dehydrating the phenate under reduced pressure, and carrying out carboxylation reaction with CO2 gas to obtain 3,6-dichlorosalicylate; and acidifying the 3,6-dichlorosalicylate to obtain the 3,6-dichlorosalicylic acid. The invention does not use any solvent or abundant catalyst, simplifies the techniques, reduces the emission of three wastes, and lowers the cost; and the invention improves the reaction steps and conditions, enhances the yield, lowers the reaction difficulty, and has high popularization value.
Description
Technical field
The present invention relates to a kind of preparation method of 3,6-dichlorosalicylic acid, particularly one is theoretical based on gas-solid reaction, shortens preparation flow, improves the preparation method of 3,6-dichlorosalicylic acids of one-step reaction yield.
Background technology
3,6-dichlorosalicylic acid is light gray slightly phenol taste solid, and fusing point is 181-183 DEG C, is the main raw material of the chloro-O-Anisic Acid of manufacture 3,6-bis-(dicamba 98).Dicamba 98 belongs to benzoic acids weedicide, has Uptake and translocation effect, has remarkable preventive effect to annual and perennial broadleaf weed, and safer to gramineous crops such as wheat, corn, millet, paddy rice.How efficient dicamba 98 is a kind of weedicide of efficient, low toxicity, wide spectrum, and at present at home for being used widely, its market requirement is all right, therefore, and simple synthesis key intermediate 3,6-dichlorosalicylic acid is very worth research.
Current 3, the synthetic method of 6-dichlorosalicylic acid is mainly with 2,5-chlorophenesic acid is initiator, in a solvent with alkali substance reaction, then dewater, salify, and then proceed in autoclave and under 4Mpa-6Mpa pressure, add the catalyzer such as salt of wormwood or triethylamine carry out carboxylation, carboxylation is complete, and then acidified product and catalyzer obtain product with 2,5-residual Dichlorophenols to isolate solvent.There is flow process complexity, aftertreatment trouble in this technique, expends the problem that solvent and catalyzer and single step yield are low.
Patent CN201010584645.6 discloses a kind of preparation technology of herbicide dicamba, this patent is with 2,5-chlorophenesic acid is raw material, by 2, after 5-chlorophenesic acid makes corresponding phenol sodium, complete carboxylation reaction in the supercritical state and obtain 3,6-dichlorosalicylic acid, then be that reagent completes with methylcarbonate
o-methylate obtained product dicamba 98.Namely this patent is adopt above-described method synthesis 3, the 6-dichlorosalicylic acid generally adopted now, and according to the record of specification sheets, the productive rate of gained 3,6-dichlorosalicylic acid is about 85%.
Summary of the invention
The present invention, in order to overcome the deficiencies in the prior art, provides a kind of route short, and technique is simple, and the preparation method of 3, the 6-dichlorosalicylic acids that the three wastes are few, this method also improves dicamba 98 competitive power in the market.
The invention discloses a kind of 3,6-dichlorosalicylic acid new preparation process, with 2,5-Dichlorophenol is raw material, add solid inorganic alkali (such as potassium hydroxide) and make it reaction salify (such as phenol sylvite), fully after completion of the reaction, be placed in high temperature negative pressure dehydration in gas-solid reactor, dewater complete, with CO under high-temperature low-pressure (with existing 4Mpa-6Mpa high pressure phase ratio) condition
2carry out carboxylation reaction, 2,5-chlorophenesic acid of constantly discharge water outlet and generation in reaction process, react complete, be directly dissolved in water, acid adding crystallization obtains 3,6-dichlorosalicylic acid.This technique not only flow process is simple, and the three wastes are few, and working pressure is low, and yield is high, significantly reduce production cost, have very high promotional value.Realize concrete technical scheme of the present invention as follows:
A kind of preparation method of 3,6-dichlorosalicylic acid, is characterized in that comprising the following steps:
(1) solid 2,5-chlorophenesic acid is fully mixed with solid inorganic alkali, make it reaction generation 2,5-dichlorobenzene phenates;
(2) step (1) reacted material is proceeded in reactor carry out decompression dehydration, will the water removing that generates of reaction;
(3), after dehydration, in reactor, CO is passed into
2gas carries out carboxylation reaction, obtains 3,6-dichlorosalicylic acid salt;
(4) after completion of the reaction, by gained 3,6-dichlorosalicylic acid salt water dissolution, be acidified with acid, then filter, wash, dry 3,6-dichlorosalicylic acid.
In above-mentioned steps (1), preferred mineral alkali is potassium hydroxide.
In step (1), the mol ratio of 2,5-chlorophenesic acid and mineral alkali is 1:0.8-3, and generally in actual production, the mol ratio of 2,5-chlorophenesic acid and mineral alkali is within the scope of 1:1-1.1.
In above-mentioned steps (1), the temperature of reaction of 2,5-chlorophenesic acid and mineral alkali is 30 DEG C-90 DEG C, preferably 60 DEG C-90 DEG C.
In above-mentioned steps (1), according to the difference of temperature of reaction, the General reactions time is 0.5h-3h.
In above-mentioned steps (2), dewatering pressure is-0.05 ~-0.098Mpa, and material is warming up to 160-200 DEG C of stopping from 60 DEG C at reduced pressure conditions, and then insulation is complete to dehydration.
In above-mentioned steps (3), during carboxylation reaction, keep CO
2reaction pressure is 0.6-1Mpa, and temperature of reaction is 160-240 DEG C, and the reaction times is 4-12 hour.
In step (3), generally after dehydration, first in reactor, pass into the carbon dioxide that pressure is 0.4Mpa-1Mpa, then emptying, other gases in still are driven out of, and then pass into CO in reactors by this operation twice repeatedly
2gas is to 0.6Mpa-1Mpa, and gas-solid reaction is carried out in airtight intensification.
In above-mentioned steps (3), preferred discontinuity exhaust during carboxylation reaction, discharges the water produced in system and a small amount of by-product phenol simultaneously, eliminates phenol recovery process, simplify operation, improve productive rate.Gross exhaust gas is for pouring CO
25%-10%, the gas of releasing discharges after condenser condenses, and the phlegma obtained in condenser is 2,5-chlorophenesic acid, 2,5-chlorophenesic acid is recycled.
The invention has the beneficial effects as follows:
1, do not use solvent and a large amount of catalyzer in whole preparation process, save solvent and catalyst consumption and discharge, decrease the aftertreatment of solvent and catalyzer, simplify technique, improve the utilization ratio of equipment simultaneously, improve operating environment, greatly reduce production cost.
2, well-known, if there is the existence of moisture in carboxylation reaction, greatly reaction yield can be reduced, and content of the present invention is owing to having taken away the water in system in interval exhaust process, make in reaction process, to avoid the existence because of moisture, and affect yield, improve reaction yield.
3, carboxylation reaction is gas-solid reaction, and reaction pressure is down to below 1MPa by the 4-6MPa of original technique, makes condition more gentle easy, and then also improves safety coefficient, save facility investment.
4, material subsequent disposal mode is simple, reacts complete and is directly dissolved in water, then acidifying qualified product.
5, whole preparation process flow process is simple, the three wastes are few, working pressure is low, yield is high, production cost is low, has very high promotional value.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.It is to be understood that following explanation is only to explain the present invention, its content is not limited.
embodiment 1
In 2L kneader, add 2, the 5-chlorophenesic acid that 329.3g massfraction is 99%, then add 124.4g massfraction be 90% potassium hydroxide solid make phenol and potassium hydroxide mol ratio be 1:1, start kneading operation afterwards.Maintaining temperature of reaction is 70 DEG C-80 DEG C, mediates 2 hours, then cooling discharge.Obtain material 452.6g.
embodiment 2
In Example 1, material 226.3g proceeds to the high pressure gas-solid reactor of 400ml.After proceeding to, still is airtight, then vacuumize and start the dehydration that heats up, dewatering pressure maintenance-0.09Mpa, material heats up from 60 DEG C, treats that temperature rises to 180 DEG C, and insulation 30min, then lays down vacuum, start to lead to CO to the inside
2gas is to pressure to 0.6Mpa, emptying, then repeats to rush once emptying.Pass into CO afterwards
2to 0.6Mpa, closed reactor starts to heat up.Insulation reaction 5h after being warming up to 200 DEG C, during reaction keeps still internal pressure to be 0.6Mpa always.Meanwhile, during reaction discontinuity discharge gas, to get rid of water and 2, the 5-chlorophenesic acid of reaction generation, amount to Exhaust Gas 5.1L, period is by filling into new CO
2maintain reaction pressure.Expellant gas reclaims 2,5-chlorophenesic acid 2.4g after condensation, moisture 2.3% in 2,5-chlorophenesic acid.Be incubated complete, cooling, emptying step-down, adds 400g water rising temperature for dissolving product, then acidifying, filtration, washing, dry 3,6-dichlorosalicylic acid 194.3g, content 98.2%, yield 92.2%.
embodiment 3
In Example 1, material 226.3g proceeds to the high pressure gas-solid reactor of 400ml.After proceeding to, still is airtight, then vacuumize and start the dehydration that heats up, dewatering pressure maintenance-0.098Mpa, material heats up from 60 DEG C, treats that temperature rises to 160 DEG C, is incubated 1 hour, then lays down vacuum, start to lead to CO to the inside
2gas is to pressure to 0.4Mpa, emptying, then repeats to rush once emptying.Pass into CO afterwards
2to 0.8Mpa, closed reactor starts to heat up.Be warming up to 180 DEG C, maintain still pressure for 0.8Mpa, start to be incubated 6h.Period discontinuity exhaust body, amount to Exhaust Gas 5.5L, and interval fills into new CO
2maintain reaction pressure.Expellant gas reclaims 2,5-Dichlorophenol 2.1g after condensation.Moisture 1.3% in chlorophenol.Be incubated complete, cooling, emptying.Add 400g water rising temperature for dissolving product, then acidifying, filtration, washing, dry 3,6-dichlorosalicylic acid 196.3g, content 98.4%, yield 93.3%.
embodiment 4
In 2L kneader, add 2, the 5-chlorophenesic acid that 329.3g massfraction is 99%, then add the potassium hydroxide solid that 110g massfraction is 90%, make phenol and potassium hydroxide mol ratio be 1:0.886, start kneading operation afterwards.Maintaining temperature of reaction is 80 DEG C-90 DEG C, mediates 1 hour, then cooling discharge.Obtain material 438.3g.
Get and mediate the high pressure gas-solid reactor that complete material 219.1g proceeds to 400ml.After proceeding to, still is airtight, then vacuumize and start the dehydration that heats up, dewatering pressure is-0.085Mpa, and material heats up from 60 DEG C, treats that temperature rises to 200 DEG C, is incubated 1 hour, then lays down vacuum, start to lead to CO to the inside
2gas is to pressure to 1Mpa, emptying, then repeats to rush once emptying.Pass into CO afterwards
2to 1Mpa, closed reactor starts to heat up.Be warming up to 240 DEG C, maintaining still pressure is 1 Mpa, starts to be incubated 4h.Period discontinuity discharge gas, and use new CO
2punching press to 1 Mpa, amounts to Exhaust Gas 10L.Expellant gas reclaims 2,5-Dichlorophenol (i.e. 2,5-chlorophenesic acid, lower same) 20.1g after condensation.Moisture 2.2% in chlorophenol.Be incubated complete, cooling, emptying.Add 400g water rising temperature for dissolving product, then acidifying, filtration, washing, dry 3,6-dichlorosalicylic acid 181.6g, content 98.7%, single step yield 86.6%.By analysis, the reason that this step yield is low is because the consumption of alkali is lower, makes unreacted 2,5-Dichlorophenols more.
embodiment 5
In 2L kneader, add 2, the 5-chlorophenesic acid that 329.3g massfraction is 99%, then add the sodium hydrate solid that massfraction is 90%, make phenol and sodium hydroxide mol ratio be 1:1.5, start kneading operation afterwards.Maintaining temperature of reaction is 30 DEG C-40 DEG C, mediates 3 hours, then cooling discharge.Obtain material 513.4g.
Get and mediate the high pressure gas-solid reactor that complete material 245.3g proceeds to 400ml.After proceeding to, still is airtight, then vacuumize and start the dehydration that heats up, dewatering pressure is-0.05Mpa, and material heats up from 60 DEG C, treats that temperature rises to 180 DEG C, is incubated 1 hour, then lays down vacuum, start to lead to CO to the inside
2gas is to pressure to 0.8Mpa, emptying, then repeats to rush once emptying.Pass into CO afterwards
2to 0.8Mpa, closed reactor starts to heat up.Be warming up to 160 DEG C, maintaining still pressure is 0.8 Mpa, starts to be incubated 10h.Period discontinuity discharge gas, and use new CO
2punching press, to 0.8Mpa, amounts to Exhaust Gas 8L.Expellant gas reclaims 2,5-Dichlorophenol 3.5g after condensation.Moisture 1.5% in chlorophenol.Be incubated complete, cooling, emptying.Add 400g water rising temperature for dissolving product, then acidifying, filtration, washing, dry 3,6-dichlorosalicylic acid 192.3g, content 98.5%, single step yield 91.4%.
embodiment 6
In 2L kneader, add 2, the 5-chlorophenesic acid that 329.3g massfraction is 99%, then add the potassium hydroxide solid that massfraction is 90%, make phenol and potassium hydroxide mol ratio be 1:3, start kneading operation afterwards.Maintaining temperature of reaction is 70 DEG C-80 DEG C, mediates 1 hour, then cooling discharge.Obtain material 701.8g.
Get and mediate the high pressure gas-solid reactor that complete material 350.9g proceeds to 400ml.After proceeding to, still is airtight, then vacuumize and start the dehydration that heats up, dewatering pressure maintenance-0.08Mpa, material heats up from 60 DEG C, treats that temperature rises to 180 DEG C, is incubated 1 hour, then lays down vacuum, start to lead to CO to the inside
2gas is to pressure to 0.8Mpa, emptying, then repeats to rush once emptying.Pass into CO afterwards
2to 0.8Mpa, closed reactor starts to heat up.Be warming up to 200 DEG C, maintain still pressure for 0.8Mpa, start to be incubated 6h.Period discontinuity exhaust body, amount to Exhaust Gas 6.5L, and interval fills into new CO
2maintain reaction pressure.Expellant gas reclaims 2,5-Dichlorophenol 2.0g after condensation.Moisture 1.3% in chlorophenol.Be incubated complete, cooling, emptying.Add 400g water rising temperature for dissolving product, then acidifying, filtration, washing, dry 3,6-dichlorosalicylic acid 197.2g, content 98.3%, yield 93.7%.
Known by above embodiment, adopt this novel method can obtain 3,6-dichlorosalicylic acid by 2,5-chlorophenesic acid is high-quality, flow process is simple, operational safety, good product quality, total recovery is high, without the need to adding the auxiliary items such as solvent, catalyzer, reduce consumption, reduce post-processing difficulty, there is higher promotional value.
Claims (8)
1. the preparation method of a dichlorosalicylic acid, is characterized in that comprising the following steps:
(1) solid 2,5-chlorophenesic acid is fully mixed with solid inorganic alkali, under solvent-free existence, make it reaction generation 2,5-dichlorobenzene phenates;
(2) step (1) reacted material is proceeded in reactor carry out decompression dehydration, will the water removing that generates of reaction;
(3), after dehydration, in reactor, CO is passed into
2gas carries out carboxylation reaction, obtains 3,6-dichlorosalicylic acid salt;
(4) after completion of the reaction, by gained 3,6-dichlorosalicylic acid salt water dissolution, be acidified with acid, then filter, wash, dry 3,6-dichlorosalicylic acid;
In step (1), the mol ratio of 2,5-chlorophenesic acid and mineral alkali is 1:0.8-3;
In step (3), during carboxylation reaction, keep CO
2reaction pressure is 0.6-1Mpa, and temperature of reaction is 160-240 DEG C, and the reaction times is 4-12 hour.
2. preparation method according to claim 1, is characterized in that: in step (1), and described mineral alkali is potassium hydroxide.
3. preparation method according to claim 1, is characterized in that: in step (1), and the mol ratio of 2,5-chlorophenesic acid and mineral alkali is 1:1-1.1.
4. preparation method according to claim 1 and 2, is characterized in that: in step (1), and the temperature of reaction of 2,5-chlorophenesic acid and mineral alkali is 30 DEG C-90 DEG C, and the reaction times is 0.5h-3h.
5. preparation method according to claim 4, is characterized in that: in step (1), and the temperature of reaction of 2,5-chlorophenesic acid and mineral alkali is 60 DEG C-90 DEG C.
6. preparation method according to claim 1, is characterized in that: in step (2), and dewatering pressure is-0.05 ~-0.098Mpa, and material is warming up to 160-200 DEG C from 60 DEG C at this pressure, and then insulation is complete to dehydration.
7. preparation method according to claim 1, is characterized in that: in step (3), after dehydration, first in reactor, pass into the carbon dioxide that pressure is 0.4Mpa-1Mpa, then emptying, this operation twice repeatedly, other gases in still are driven out of, and then pass into CO in reactor
2gas is to 0.6Mpa-1Mpa, and gas-solid reaction is carried out in airtight intensification.
8. preparation method according to claim 1, is characterized in that: in step (3), and discontinuity exhaust during carboxylation reaction, gross exhaust gas is for being filled with CO
25%-10%, the gas of releasing discharges after condenser condenses, and the phlegma obtained in condenser is 2,5-chlorophenesic acid, 2,5-chlorophenesic acid is recycled.
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| EP3303227B1 (en) | 2015-06-03 | 2020-06-24 | Monsanto Technology LLC | Separation of dichlorophenols |
| EP3551601A4 (en) | 2016-12-07 | 2020-08-05 | Monsanto Technology LLC | Processes for purification, recovery, and conversion of chlorophenol salts and preparation and recovery of products prepared therefrom |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617338A (en) * | 2012-02-29 | 2012-08-01 | 常州市阳光药业有限公司 | Preparation method of p-trifluoromethyl salicylic acid |
| CN103012124A (en) * | 2012-12-26 | 2013-04-03 | 浙江大学 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
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| JP2004123592A (en) * | 2002-10-01 | 2004-04-22 | Ueno Seiyaku Oyo Kenkyusho:Kk | Method for producing hydroxybenzoic acid compound |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617338A (en) * | 2012-02-29 | 2012-08-01 | 常州市阳光药业有限公司 | Preparation method of p-trifluoromethyl salicylic acid |
| CN103012124A (en) * | 2012-12-26 | 2013-04-03 | 浙江大学 | Preparation method of 3,6-dichloro-2-hydroxybenzoic acid |
Non-Patent Citations (1)
| Title |
|---|
| 孟明扬等.《3, 6 一二氯水杨酸的合成》.《精细与专用化学品》.2003,(第15期), * |
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Address after: No. 03001, chlor alkali Road, Weifang Coastal Economic Development Zone, Shandong, Shandong Patentee after: Shandong Weifang Rainbow Chemical Co.,Ltd. Address before: Haiyuan Binhai Economic Development Zone, Shandong province Weifang city 262737 Street No. 600 Patentee before: Shandong Weifang Rainbow Chemical Co.,Ltd. |