CN108947803A - A kind of preparation method of phenoxy carboxylic acid substance - Google Patents
A kind of preparation method of phenoxy carboxylic acid substance Download PDFInfo
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- CN108947803A CN108947803A CN201810226098.0A CN201810226098A CN108947803A CN 108947803 A CN108947803 A CN 108947803A CN 201810226098 A CN201810226098 A CN 201810226098A CN 108947803 A CN108947803 A CN 108947803A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/285—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with peroxy-compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/363—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Abstract
The present invention provides the preparation methods of phenoxy carboxylic acid substance, include: S1) halogenated aliphatic alcohol shown in phenol compound shown in formula (I), formula (II) is mixed in organic solvent with alkali carbonate, heating reaction, obtains benzene oxygen fatty alcohol；S2) by the benzene oxygen fatty alcohol and oxidant reaction, benzene oxygen fatty acid is obtained；S3) by the benzene oxygen fatty acid, chlorination catalyst and chlorinating agent hybrid reaction, phenoxy carboxylic acid substance shown in formula (III) is obtained.Compared with prior art, the present invention obtains benzene oxygen fatty alcohol using phenol compound as starting material, it is aoxidized and obtains phenoxy carboxylic acid compound after chlorination reaction, this method is without dehydration, and environmental-friendly, no chlorophenol participation will not generate dioxin, also solve the problems, such as that smell is big, and oriented chlorination selectivity is high, while this method is not necessarily to cumbersome concentration unit, overall flow is simple, equipment investment is few, and energy consumption reduces.
Description
Technical field
The invention belongs to technical field of organic synthesis more particularly to a kind of preparation methods of phenoxy carboxylic acid substance.
Background technique
Currently, phenoxy carboxylic acid substance is widely used in herbicide pesticide.Nineteen forty-one has synthesized first phenoxy carboxylic acid and has removed
The kind 2 of careless agent, 4- dichlorphenoxyacetic acid, nineteen forty-two have found that the compound has the function of plant hormone, nineteen forty-four discovery
2,4- dichlorphenoxyacetic acids and 2,4,5- tears have activity of weeding, 2 first of discovery herbicide, 4 chlorine in 1945 to field bindweed.It is such to remove
Selectivity, conductibility and the removing activity that careless agent is shown become the basis of herbicide development thereafter, promote the hair of chemical weed control
Exhibition.
Difference of the phenoxy carboxylic acid herbicides according to its active constituent body compound can be divided into two different fundamental systems
Column.One is being ontology with 2,4- Dichlorophenol, such as 2,4- dichlorphenoxyacetic acid (2,4- drops acid), 2,4- Dichlorophenoxy propionic acid
(2,4- drop P), 2,4 dichloro benzene oxy butyrate (2,4- drop B)；Another kind is such as 2 first, 4 chloric acid using o-cresol as ontology
(MCPA), Vi par (MCPP), Thistrol (MCPB).
The synthetic method of 2,4- Dichlorophenoxy carboxylic acid disclosed in the prior art mainly uses Williamson condensation method, production
Technique is: chlorophenesic acid, at salt, then carries out in water phase with chlorinated carboxylic acid, alkali neutralization at salt product again in water phase
Williamson condensation reaction obtains benzene oxycarboxylic acid salt, is then acidified again, obtains raw medicine after obtaining benzene oxycarboxylic acid filtering drying.
But such method has the disadvantage in that, 1) from raw material, which obtains 2,4- dichloro-benzenes using phenol chlorination
Phenol, 2,4- chlorophenesic acid smells are very big, and hypertoxic carcinogen dioxin is generated when condensation；2) from process flow, the technique
Process is complicated, and first chlorination obtains chlorophenol, then synthesizes phenol sodium, and monoxone configuration neutralizes material, is then condensed, is acidified, process is complicated；
3) environmentally friendly disadvantage, the technique are carried out in water phase using phenol sodium and chlorinated carboxylic acid sodium, chlorinated carboxylic acid sodium pole under alkali cleaning water environment
It is high to lead to chlorinated carboxylic acid sodium waste, and then leads to high organic content in waste water for facile hydrolysis, and wastewater flow rate is big.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of preparation side of benzene oxycarboxylic acid ester type compound
Method, the preparation method is simple and yield is higher.
The present invention provides a kind of preparation methods of phenoxy carboxylic acid substance, comprising:
S1) halogenated aliphatic alcohol shown in phenol compound shown in formula (I), formula (II) and alkali carbonate are being had
It is mixed in solvent, heating reaction obtains benzene oxygen fatty alcohol；
S2) by the benzene oxygen fatty alcohol and oxidant reaction, benzene oxygen fatty acid is obtained；
S3) by the benzene oxygen fatty acid, chlorination catalyst and chlorinating agent hybrid reaction, benzene oxygen shown in formula (III) is obtained
Carboxylic-acid substance；
Wherein, R is the alkyl of H or C1~C5；R1For the alkyl of H or C1~C4；
R2For Cl or H, and R and R2It is not simultaneously H；X is halogen.
Preferably, the alkali carbonate is selected from one of sodium carbonate, potassium carbonate and cesium carbonate or a variety of.
Preferably, halogenated aliphatic alcohol and alkali metal carbonic acid shown in phenol compound, formula (II) shown in the formula (I)
The molar ratio of salt is 1:(0.98~1.5): (0.98~1.5).
Preferably, after reaction, filtrate rectification process after filtering, is obtained benzene oxygen fatty alcohol by cooling for heating.
Preferably, the step S2) in be additionally added oxidation catalyst；The oxidation catalyst is selected from active carbon, white carbon black
With one of molecular sieve carried metal salt or a variety of；The quality of the oxidation catalyst be benzene oxygen fatty alcohol quality 1%~
10%.
Preferably, the oxidant is selected from one of hydrogen peroxide, oxygen and ozone or a variety of；The benzene oxygen fatty alcohol with
The molar ratio of oxidant is 1:(1~2).
Preferably, the step S1) in heating reaction temperature be 80 DEG C~160 DEG C；The time of the heating reaction is 2
~for 24 hours；
The step S2) in react temperature be 80 DEG C~180 DEG C；The time of the reaction be 2~for 24 hours.
Preferably, the chlorinating agent is selected from chlorine, thionyl chloride, chlorosulfuric acid, phosgene and two (trichloromethyl) carbonic esters
One of or it is a variety of.
Preferably, the chlorination catalyst is selected from one of formamide, acetamide and n,N-Dimethylformamide or more
Kind.
Preferably, the step S2) in after reaction, after cooling filtering, chlorination catalyst and chlorinating agent hybrid reaction is added,
Obtain phenoxy carboxylic acid substance shown in formula (III).
The present invention provides a kind of preparation methods of phenoxy carboxylic acid substance, comprising: S1) by phenol shown in formula (I)
Halogenated aliphatic alcohol shown in compound, formula (II) mixes in organic solvent with alkali carbonate, and heating reaction obtains benzene oxygen
Fatty alcohol；S2) by the benzene oxygen fatty alcohol and oxidant reaction, benzene oxygen fatty acid is obtained；S3) by the benzene oxygen fatty acid, chlorine
Change catalyst and chlorinating agent hybrid reaction, obtains phenoxy carboxylic acid substance shown in formula (III)；Wherein, R is H's or C1~C5
Alkyl；R1For the alkyl of H or C1~C4；R2For Cl or H, and R and R2It is not simultaneously H；X is halogen.Compared with prior art, originally
Invention obtains benzene oxygen fatty alcohol using phenol compound as starting material, is aoxidized and obtains phenoxy carboxylic acid after chlorination reaction
Compound, this method is without dehydration, and environmental-friendly, the participation of no chlorophenol will not generate dioxin, also solves that smell is big to ask
Topic, and oriented chlorination selectivity is high, while this method is not necessarily to cumbersome concentration unit, overall flow is simple, and equipment investment is few, energy
Consumption reduces.
Detailed description of the invention
Fig. 1 is the liquid chromatogram of 2,4 dichlorophenoxyacetic acid obtained in the embodiment of the present invention 2.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods of phenoxy carboxylic acid substance, comprising:
S1) halogenated aliphatic alcohol shown in phenol compound shown in formula (I), formula (II) and alkali carbonate are being had
It is mixed in solvent, heating reaction obtains benzene oxygen fatty alcohol；
S2) by the benzene oxygen fatty alcohol and oxidant reaction, benzene oxygen fatty acid is obtained；
S3) by the benzene oxygen fatty acid, chlorination catalyst and chlorinating agent hybrid reaction, benzene oxygen shown in formula (III) is obtained
Carboxylic-acid substance；
Wherein, R is the alkyl of H or C1~C5, the preferably alkyl of C1~C3, the more preferably alkyl of C1~C2, then excellent
It is selected as methyl；R1For the alkyl of H or C1~C4, the alkyl of the alkyl of preferably H or C1~C3, more preferably H or C1~C2；R2
For Cl or H, and R and R2It is not simultaneously H；X is halogen, preferably Cl.
The present invention is not particularly limited the source of all raw materials, is commercially available.
By halogenated aliphatic alcohol shown in phenol compound shown in formula (I), formula (II) and alkali carbonate organic
It is mixed in solvent；The alkali carbonate is alkali carbonate well known to those skilled in the art, and it is special to have no
It limits, is preferably one of sodium carbonate, potassium carbonate and cesium carbonate or a variety of in the present invention；Phenol shown in the formula (I)
The molar ratio of halogenated aliphatic alcohol shown in compound, formula (II) and alkali carbonate is preferably 1:(0.98~1.5): (0.98
~1.5), more preferably 1:(1~1.2): (1~1.2) is further preferably 1:1:(1~1.2)；The organic solvent is this field
Organic solvent known to technical staff has no special limitation, is preferably aprotic polar solvent in the present invention, more preferably
For N,N-dimethylformamide and/or dimethyl sulfoxide.
After mixing, heating reaction；The temperature of the heating reaction is preferably 80 DEG C~160 DEG C, more preferably 100 DEG C~
160 DEG C, be further preferably 120 DEG C~160 DEG C, most preferably 130 DEG C~150 DEG C；The time of the heating reaction is preferably 2~
For 24 hours, more preferably 5~15h is further preferably 5~10h.
After heating reaction, preferably cools down, after filtering, by filtrate rectification process, obtain benzene oxygen fatty alcohol；The cooling is preferred
It is down to room temperature；Filtering can preferably use organic solvent washing filter cake, cleaning solution and filtrate are closed except the salt that dereaction generates after filtering
And carry out rectification process；The organic solvent is same as above, and details are not described herein；The solvent that the rectification process obtains is recyclable
It applies.
By the benzene oxygen fatty alcohol and oxidant reaction；The oxidant is that oxidant well known to those skilled in the art is
Can, special limitation is had no, is preferably one of hydrogen peroxide, oxygen and ozone or a variety of in the present invention；The benzene oxygen fat
The molar ratio of alcohol and oxidant is preferably 1:(1~2), more preferably 1:(1.05~1.5), it is further preferably 1:(1.05~1.2)；
In invention, the reaction preferably existing for the oxidation catalyst under the conditions of carry out, the oxidation catalyst is those skilled in the art
Oxidation catalyst known to member, has no special limitation, in the present invention preferably active carbon, white carbon black with it is molecular sieve carried
One of metal salt is a variety of；Metal salt in the molecular sieve carried metal salt is preferably cobalt acetate/manganese acetate, manganese chloride
It is one of great or a variety of with chlorination；The quality of the oxidation catalyst is preferably the 1%~10% of benzene oxygen fatty alcohol quality, more
Preferably 2%~8%, it is further preferably 2%~5%；The temperature of the reaction is preferably 80 DEG C~180 DEG C, more preferably 100 DEG C
~160 DEG C, be further preferably 120 DEG C~140 DEG C；The time of the reaction is preferably 2~for 24 hours, more preferably 10~20h, then it is excellent
It is selected as 12~14h.
After reaction, it preferably filters, recycles catalyst, filtrate directly cools down, preferably cools down without carrying out product separation
To 60 DEG C~120 DEG C, 80 DEG C~100 DEG C are more preferably cooled to, chlorination catalyst and chlorinating agent hybrid reaction is added；The chlorination
Catalyst is chlorination catalyst well known to those skilled in the art, has no special limitation, is preferably amide in the present invention
One of class catalyst, more preferably formamide, acetamide and n,N-Dimethylformamide are a variety of；The chlorination catalyst
Quality be preferably the 1%~5% of benzene oxygen fatty acid quality；The chlorinating agent is that chlorinating agent well known to those skilled in the art is
Can, special limitation is had no, is preferably chlorine, thionyl chloride, chlorosulfuric acid, phosgene (phosgene) and two (three chloromethanes in the present invention
Base) one of carbonic ester (solid phosgene) or a variety of；The molar ratio of the benzene oxygen fatty acid and chlorinating agent be preferably 1:(1~
2.5), more preferably 1:(1~2.2)；The time of the hybrid reaction is preferably 0.1~1 hour.
After hybrid reaction, cooling is dry after filtering, obtains phenoxy carboxylic acid substance shown in formula (III).
The present invention obtains benzene oxygen fatty alcohol using phenol compound as starting material, is aoxidized and is obtained after chlorination reaction
Phenoxy carboxylic acid compound, this method is without dehydration, and environmental-friendly, no chlorophenol participation will not generate dioxin, also solves
The big problem of smell, and oriented chlorination selectivity is high, while this method is not necessarily to cumbersome concentration unit, overall flow is simple, if
Standby small investment, energy consumption reduce.
In order to further illustrate the present invention, with reference to embodiments to a kind of phenoxy carboxylic acid substance provided by the invention
Preparation method is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
The phenol of 97g 98.5%, the chlorethanol of 81g 99%, 99% potassium carbonate of 145g are reacted with 300g DMF addition
In device, 130 DEG C are warming up to, insulation reaction 6 hours, room temperature is cooled to, is then filtered to remove salt, fresh DMF is added to wash twice
Then filter cake obtains Phenoxyethanol after mixed filtrate rectification process, then by 139.6g (1mol) Phenoxyethanol, water 300g, plus
Enter 14g active carbon, the hydrogen peroxide of 350g 10% be added, is warming up to 120 DEG C or so and is kept for 12 hours, check Phenoxyethanol content,
After Phenoxyethanol content is less than 0.1%, 80 DEG C or so are cooled to, 1.4g formamide is added, is passed through 144g chlorine, duration of ventilation
Control cools down after 2~5 hours are to be chlorinated, and 2,4- dichlorphenoxyacetic acid 214.1g is dried to obtain in filtering, purity 98.2%,
Yield 95.1%.
Embodiment 2:
Reaction is added in the phenol of 97g 98.5%, the chlorethanol of 81g 99%, 99% potassium carbonate of 145g, 300g DMSO
In device, 150 DEG C are warming up to, 5 hours is kept the temperature, cools to room temperature, be then filtered to remove salt, fresh DMSO is added to wash twice of filter
Then cake obtains Phenoxyethanol after mixed filtrate rectification process, Phenoxyethanol 139.6g (1mol), water 300g, addition 28g is white
Carbon black is passed through 32g ozone, is warming up to 120 DEG C or so and is kept for 12 hours, Phenoxyethanol content is checked, when Phenoxyethanol content is small
In 0.1% after not turning qualification.80 DEG C or so are cooled to, 1.5g formamide is added, 270g chlorosulfuric acid, time for adding control is added dropwise
System cools down after 2~5 hours to be chlorinated, filtering, dries to obtain 2,4- dichlorphenoxyacetic acid 217.4g, and purity 98.1% is received
Rate 96.6%.
2,4- dichlorphenoxyacetic acid obtained in embodiment 2 is analyzed using high performance liquid chromatography, obtains its liquid phase
Chromatogram is shown in Table 1 as shown in Figure 1, obtaining liquid chromatography results.
1 liquid chromatography results of table
| Peak number | Retention time | Area | Highly | Area % |
| 1 | 2.228 | 9268 | 389 | 0.065 |
| 2 | 2.809 | 35812 | 3969 | 0.253 |
| 3 | 4.083 | 1660 | 184 | 0.012 |
| 4 | 4.702 | 11828 | 876 | 0.083 |
| 5 | 6.186 | 7996 | 565 | 0.056 |
| 6 | 9.435 | 14105413 | 788834 | 99.53 |
| It amounts to | - | 14171977 | 794818 | 100 |
Embodiment 3
The o-cresol of 109g 98.5%, the chlorethanol of 81g 99%, 99% potassium carbonate of 145g and 300g DMF are added
In reactor, 130 DEG C are warming up to, insulation reaction 6 hours, room temperature is cooled to, is then filtered to remove salt, fresh DMF is added to wash
Then twice of filter cake obtains Phenoxyethanol after mixed filtrate rectification process, then by 153.6g (1mol) Phenoxyethanol, water
300g, 16g active carbon is added, the hydrogen peroxide of 350g10% is added, be warming up to 120 DEG C or so and kept for 12 hours, check adjacent toluene
Oxyethanol content is cooled to 80 DEG C or so after adjacent toluene oxyethanol content is less than 0.1%, and 1.4g formamide is added, is passed through
72g chlorine, duration of ventilation control after 2~5 hours to be chlorinated, cool down, and 2 first, 4 chlorophenoxyacetic acid is dried to obtain in filtering
193.5g, purity 98.1%, yield 95.3%.
Embodiment 4
The o-cresol of 109g 98.5%, the chlorethanol of 81g 99%, 99% potassium carbonate of 145g, 300g DMSO are added
In reactor, 150 DEG C are warming up to, 5 hours is kept the temperature, cools to room temperature, be then filtered to remove salt, fresh DMSO is added to wash twice
Then filter cake obtains Phenoxyethanol after mixed filtrate rectification process, by adjacent toluene oxyethanol 154.4g, water 300g, 34g charcoal is added
It is black, it is passed through 32g ozone, 120 DEG C or so is warming up to and is kept for 12 hours, adjacent toluene oxyethanol content is checked, when adjacent toluene oxyethanol
After content is less than 0.1%, 80 DEG C or so are cooled to, 1.5g formamide is added, 136g chlorosulfuric acid is added dropwise, time for adding is controlled 2
After~5 hours to be chlorinated, cool down, 2 first 4-chlorophenoxyacetic acid 194.1g, purity 98.1%, yield are dried to obtain in filtering
96.6%.
Claims (10)
1. a kind of preparation method of phenoxy carboxylic acid substance characterized by comprising
S1) by halogenated aliphatic alcohol shown in phenol compound shown in formula (I), formula (II) and alkali carbonate organic molten
It is mixed in agent, heating reaction obtains benzene oxygen fatty alcohol；
S2) by the benzene oxygen fatty alcohol and oxidant reaction, benzene oxygen fatty acid is obtained；
S3) by the benzene oxygen fatty acid, chlorination catalyst and chlorinating agent hybrid reaction, benzene oxycarboxylic acid shown in formula (III) is obtained
Substance；
Wherein, R is the alkyl of H or C1~C5；R1For the alkyl of H or C1~C4；
R2For Cl or H, and R and R2It is not simultaneously H；X is halogen.
2. preparation method according to claim 1, which is characterized in that the alkali carbonate is selected from sodium carbonate, carbonic acid
One of potassium and cesium carbonate are a variety of.
3. preparation method according to claim 1, which is characterized in that phenol compound, formula shown in the formula (I)
(II) molar ratio of halogenated aliphatic alcohol and alkali carbonate shown in is 1:(0.98~1.5): (0.98~1.5).
4. preparation method according to claim 1, which is characterized in that after reaction, cooling after filtering, will filter for heating
Liquid rectification process obtains benzene oxygen fatty alcohol.
5. preparation method according to claim 1, which is characterized in that the step S2) in be additionally added oxidation catalyst；Institute
It states oxidation catalyst and is selected from one of active carbon, white carbon black and molecular sieve carried metal salt or a variety of；The oxidation catalyst
Quality be benzene oxygen fatty alcohol quality 1%~10%.
6. preparation method according to claim 1, which is characterized in that the oxidant is selected from hydrogen peroxide, oxygen and ozone
One of or it is a variety of；The molar ratio of the benzene oxygen fatty alcohol and oxidant is 1:(1~2).
7. preparation method according to claim 1, which is characterized in that the step S1) in heating reaction temperature be 80
DEG C~160 DEG C；It is described heating reaction time be 2~for 24 hours；
The step S2) in react temperature be 80 DEG C~180 DEG C；The time of the reaction be 2~for 24 hours.
8. preparation method according to claim 1, which is characterized in that the chlorinating agent is selected from chlorine, thionyl chloride, sulfonyl
One of chlorine, phosgene and two (trichloromethyl) carbonic esters are a variety of.
9. preparation method according to claim 1, which is characterized in that the chlorination catalyst is selected from formamide, acetamide
With one of N,N-dimethylformamide or a variety of.
10. preparation method according to claim 1, which is characterized in that the step S2) in reaction after, cooling filtering after,
Chlorination catalyst and chlorinating agent hybrid reaction is added, obtains phenoxy carboxylic acid substance shown in formula (III).
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110143861A (en) * | 2019-06-03 | 2019-08-20 | 珠海润都制药股份有限公司 | A kind of preparation method of brufen |
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| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chloration method for phenoxyacetic acid and derivatives thereof |
| CN103709036A (en) * | 2013-12-03 | 2014-04-09 | 天津久日化学股份有限公司 | Novel bifunctional benzoyl formic acid hydroxy ketone ester compounds and photoinitiators containing the compounds |
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2018
- 2018-03-19 CN CN201810226098.0A patent/CN108947803A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102336654A (en) * | 2011-07-14 | 2012-02-01 | 大连化工研究设计院 | Chloration method for phenoxyacetic acid and derivatives thereof |
| CN103709036A (en) * | 2013-12-03 | 2014-04-09 | 天津久日化学股份有限公司 | Novel bifunctional benzoyl formic acid hydroxy ketone ester compounds and photoinitiators containing the compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110143861A (en) * | 2019-06-03 | 2019-08-20 | 珠海润都制药股份有限公司 | A kind of preparation method of brufen |
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Application publication date: 20181207 |