CN108947826A - A kind of preparation method of benzene oxycarboxylic acid ester type compound - Google Patents
A kind of preparation method of benzene oxycarboxylic acid ester type compound Download PDFInfo
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- CN108947826A CN108947826A CN201810226626.2A CN201810226626A CN108947826A CN 108947826 A CN108947826 A CN 108947826A CN 201810226626 A CN201810226626 A CN 201810226626A CN 108947826 A CN108947826 A CN 108947826A
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The present invention provides a kind of preparation methods of benzene oxycarboxylic acid ester type compound, it include: to mix halogenated carboxylic ester shown in phenol compound shown in formula (I), formula (II) in organic solvent with metal powder, heating reaction, obtains benzene oxycarboxylic acid ester type compound shown in formula (III)；The metal powder is aluminium powder and/or magnesium powder；Wherein, R is the alkyl of C1~C10；R1For the alkylidene of C1~C6 of linear chain or branched chain；R2For the alkyl of C1~C10, naphthenic base or aryl；X is halogen.Compared with prior art, the present invention reacts phenol compound with halogenated carboxylic ester in anhydrous system, halogenated carboxylic acid ester hydrolysis is reduced, the generation of high-salt wastewater has been prevented, and is post-processed without dehydration, processing is simple, low energy consumption, avoids the loss because of effective component caused by being separated by solid-liquid separation, improves the yield of effective component, product purity height, high income, the hydrogen also recoverable that simultaneous reactions generate.
Description
Technical field
The invention belongs to technical field of organic synthesis more particularly to a kind of preparation methods of benzene oxycarboxylic acid ester type compound.
Background technique
2,4- dichlorphenoxyacetic acid methyl esters itself can be used as herbicide use, hydrolysate 2,4- dichlorphenoxyacetic acid
It is a kind of widely used herbicide, with the biggish market demand.
Currently, the synthetic method of 2,4- dichlorphenoxyacetic acids (2,4-D) mainly uses Williamson condensation method comprising
Etherificate and first etherificate two main road Wiring technology of afterchlorinate after first chlorination.Wherein, in the route being etherified after first chlorination, synthesis chlorophenol choosing
Selecting property is not high, needs rectification and purification, and during this section chlorinated phenol smell it is very big, also have the production of extremely toxic substance dioxin
It is raw, environment is caused greatly to damage, to when later period condensation, due to being carried out in water phase, consumption liquid alkaline is more, leads to the later period
Waste water and abraum salt amount are larger, and effect on environment is very big, are now in superseded edge.To overcome the above disadvantages, first ether is proposed
Change the production technology of afterchlorinate, Han Hong Fei in 2008 et al. is raw material by three-step reaction synthesis 2,4-D using phenol, first by phenol
The 30min that flows back under alkaline condition with monoxone generates phenoxy acetic acid, yield 91.51%；Solvent is made with dense with glacial acetic acid again
HCl/H2O2Make 55 DEG C of reaction 20min of chlorination reagent, generates p-chlorophenoxyacetic acid, yield 78.14%；Finally, being existed with sodium hypochlorite
By p-chlorophenoxyacetic acid chlorination at 2,4-D in acid medium, reaction equation is as follows:
Although the method solves the temperature of chlorophenol smell and dioxin, but there are still waste water abraum salt amounts greatly to ask
Topic.
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 benzene oxycarboxylic acid ester type compound, comprising:
By halogenated carboxylic ester shown in phenol compound shown in formula (I), formula (II) and metal powder in organic solvent
Middle mixing, heating reaction, obtains benzene oxycarboxylic acid ester type compound shown in formula (III)；The metal powder is aluminium powder and/or magnesium
Powder；
Wherein, R is the alkyl of H or C1~C10；R1For the alkylidene of C1~C6 of linear chain or branched chain；
R2For the alkyl of C1~C10, naphthenic base or aryl；X is halogen.
Preferably ,-the R1It is-CH2-、-CH(CH3)-or-(CH2)3-。
Preferably, the X is Cl.
Preferably, the R is the alkyl of C1~C3.
Preferably, halogenated carboxylic ester shown in phenol compound, metal powder shown in the formula (I) and formula (II)
Molar ratio is 2:(1~1.5): (1~1.5).
Preferably, the organic solvent is selected from dimethylformamide, dimethyl sulfoxide, acetone and 1,3- dimethyl -2- miaow
One of oxazolone is a variety of.
Preferably, the quality of the organic solvent is 2~8 times of phenol compound quality shown in formula (I).
Preferably, the temperature of the heating reaction is 80 DEG C~160 DEG C；It is described heating reaction time be 1~for 24 hours.
Preferably, after the heating reaction, filtering, distillation filtrate obtains benzene oxycarboxylic acid esters chemical combination shown in formula (III)
Object.
The present invention provides a kind of preparation methods of benzene oxycarboxylic acid ester type compound, comprising: by phenol shown in formula (I)
Halogenated carboxylic ester shown in compound, formula (II) mixes in organic solvent with metal powder, and heating reaction obtains formula (III)
Shown in benzene oxycarboxylic acid ester type compound；The metal powder is aluminium powder and/or magnesium powder；Wherein, R is the alkyl of C1~C10；R1
For the alkylidene of C1~C6 of linear chain or branched chain；R2For the alkyl of C1~C10, naphthenic base or aryl；X is halogen.With existing skill
Art is compared, and the present invention reacts phenol compound with halogenated carboxylic ester in anhydrous system, reduces the water of halogenated carboxylic ester
Solution has prevented the generation of high-salt wastewater, and post-processes without dehydration, and processing is simple, and low energy consumption, avoids because separation of solid and liquid causes
Effective component loss, improve the yield of effective component, product purity is high, high income, and the hydrogen that simultaneous reactions generate is also
Recoverable.
Detailed description of the invention
Fig. 1 is the LC-MS spectrogram of methyl phenoxyacetate obtained in the embodiment of the present invention 1.
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 benzene oxycarboxylic acid ester type compound, comprising: by phenol shown in formula (I)
Halogenated carboxylic ester shown in compound, formula (II) mixes in organic solvent with metal powder, and heating reaction obtains formula (III)
Shown in benzene oxycarboxylic acid ester type compound；The metal powder is aluminium powder and/or magnesium powder；
Wherein, R is the alkyl of H or C1~C10, the alkane of the alkyl of preferably H or C1~C5, more preferably H or C1~C3
Base is further preferably H or methyl；The R can be ortho-substituent or para-orientating group, be preferably ortho-substituent in the present invention；
R1It is further preferably straight for the alkylidene of C1~C6 of linear chain or branched chain, the more preferably alkylidene of C1~C4 of linear chain or branched chain
The alkylidene of C1~C3 of chain or branch, most preferably-CH2-、-CH(CH3)-or-(CH2)3-；R2Alkyl, ring for C1~C10
Alkyl or aryl, the preferably alkyl of C1~C6, naphthenic base or aryl, the more preferably alkyl of C1~C3, naphthenic base or aryl；
X is halogen, preferably Cl or Br, more preferably Cl.
Reaction process is as follows:
The present invention is not particularly limited the source of all raw materials, is commercially available.
By halogenated carboxylic ester shown in phenol compound shown in formula (I), formula (II) and metal powder in organic solvent
Middle mixing；The molar ratio of halogenated carboxylic ester shown in phenol compound shown in the formula (I), metal powder and formula (II) is excellent
It is selected as 2:(1~1.5): (1~1.5), more preferably 2:(1~1.2): (1~1.2) is further preferably 2:1:1；It is described organic molten
Agent is organic solvent well known to those skilled in the art, has no special limitation, is preferably aprotonic polar in the present invention
Solvent, more preferably dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone and 1,3- dimethyl -2- imidazolone
One of (DMI) or it is a variety of；The quality of the organic solvent is preferably 2~8 of phenol compound quality shown in formula (I)
Times, more preferably 2~6 times, be further preferably 2~5 times.
After mixing, heating reaction；The temperature of the heating reaction is preferably 80 DEG C~160 DEG C, more preferably 90 DEG C~140
DEG C, it is further preferably 100 DEG C~120 DEG C；The time of the heating reaction is preferably 1~for 24 hours, more preferably 5~20h, and further preferably
For 8~15h, most preferably 8~12h.
After reaction, it is preferably dropped to room temperature, is filtered, distillation filtrate obtains benzene oxycarboxylic acid esters chemical combination shown in formula (III)
Object；To reduce loss of product, cleaning solution preferably with after organic solvent washing, distillation is merged with filtrate by the filter cake being obtained by filtration；
The organic solvent is same as above, and details are not described herein.Whole process waterless operation of the invention, is filtered to remove salt after reaction, whole
A anhydrous output of process, anhydrous participation are truly realized no effuent discharge；And the hydrogen recoverable generated in reaction process.
The present invention reacts phenol compound with halogenated carboxylic ester in anhydrous system, reduces the water of halogenated carboxylic ester
Solution, has prevented the generation of high-salt wastewater, and post-processes without dehydration, and processing is simple, and low energy consumption, and equipment investment is few, avoid because
The loss of effective component caused by being separated by solid-liquid separation improves the yield of effective component, product purity height, high income, simultaneous reactions
The hydrogen of generation also recoverable.
In order to further illustrate the present invention, with reference to embodiments to a kind of benzene oxycarboxylic acid esters chemical combination provided by the invention
The preparation method of object is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment 1
By phenol 47.6g (0.5mol), DMF100g, 6.2g magnesium powder (0.252mol), methyl chloroacetate 54.8g
(0.50mol), mixing are warming up to 80 DEG C, insulation reaction 12 hours；The hydrogen generated in the process is collected with air bag.Reaction terminates
Afterwards, room temperature is cooled to, magnesium chloride is then filtered to remove, washs filter cake twice with fresh DMF, cleaning solution and filtrate are mixed and steamed
Fraction is from obtaining product 76.5g, purity 99.1%, yield 90.8%.
Methyl phenoxyacetate obtained in embodiment 1 is analyzed using LC-MS, obtains LC-MS spectrogram such as
Shown in Fig. 1.
Embodiment 2
By phenol 47.6g (0.5mol), DMF100g, 6.2g magnesium powder (0.252mol), methyl chloroacetate 54.8g
(0.50mol), mixing are warming up to 160 DEG C, insulation reaction 12 hours；The hydrogen generated in the process is collected with air bag.Reaction terminates
Afterwards, room temperature is cooled to, magnesium chloride is then filtered to remove, washs filter cake twice with fresh DMF, cleaning solution and filtrate are mixed and steamed
Fraction is from obtaining product 80.61g, purity 99.1%, yield 97.1%.
Embodiment 3
By phenol 47.6g (0.5mol), DMF100g, 9.2g aluminium powder (0.167mol), methyl chloroacetate 54.8g
(0.50mol), mixing are warming up to 160 DEG C, insulation reaction 12 hours；The hydrogen generated in the process is collected with air bag.Reaction terminates
Afterwards, room temperature is cooled to, aluminium chloride is then filtered to remove, washs filter cake twice with fresh DMF, cleaning solution and filtrate are mixed and steamed
Fraction is from obtaining product 79.61g, purity 98.9%, yield 96.2%.
Embodiment 4
By phenol 47.6g (0.5mol), DMSO100g, 9.2g aluminium powder (0.167mol), methyl chloroacetate 54.8g
(0.50mol), mixing are warming up to 160 DEG C, insulation reaction 12 hours.The hydrogen generated in the process is collected with air bag.Reaction terminates
Afterwards, room temperature is cooled to, aluminium chloride is then filtered to remove, washs filter cake twice with fresh DMSO, cleaning solution and filtrate are mixed
Distillation separation, obtains product 81.61g, purity 99.3%, yield 97.7%.
Embodiment 5
By phenol 47.6g (0.5mol), DMSO 100g, 6.2g magnesium powder (0.252mol), methyl chloroacetate 54.8g
(0.50mol), mixing are warming up to 160 DEG C, insulation reaction 12 hours.The hydrogen generated in the process is collected with air bag.Reaction terminates
Afterwards, room temperature is cooled to, magnesium chloride is then filtered to remove, washs filter cake twice with fresh DMSO, cleaning solution and filtrate are mixed
Distillation separation, obtains product 81.61g, purity 99.2%, yield 97.9%.
Claims (9)
1. a kind of preparation method of benzene oxycarboxylic acid ester type compound characterized by comprising
Halogenated carboxylic ester shown in phenol compound shown in formula (I), formula (II) and metal powder are mixed in organic solvent
It closes, heating reaction obtains benzene oxycarboxylic acid ester type compound shown in formula (III)；The metal powder is aluminium powder and/or magnesium powder；
Wherein, R is the alkyl of H or C1~C10；R1For the alkylidene of C1~C6 of linear chain or branched chain；
R2For the alkyl of C1~C10, naphthenic base or aryl；X is halogen.
2. preparation method according to claim 1, which is characterized in that-the R1It is-CH2-、-CH(CH3)-or-
(CH2)3-。
3. preparation method according to claim 1, which is characterized in that the X is Cl.
4. preparation method according to claim 1, which is characterized in that the R is the alkyl of C1~C3.
5. preparation method according to claim 1, which is characterized in that phenol compound, metal shown in the formula (I)
The molar ratio of powder and halogenated carboxylic ester shown in formula (II) is 2:(1~1.5): (1~1.5).
6. preparation method according to claim 1, which is characterized in that the organic solvent is selected from dimethylformamide, two
Methyl sulfoxide, acetone and 1, one of 3- dimethyl -2- imidazolone or a variety of.
7. preparation method according to claim 1, which is characterized in that the quality of the organic solvent is shown in formula (I)
2~8 times of phenol compound quality.
8. preparation method according to claim 1, which is characterized in that the temperature of the heating reaction is 80 DEG C~160 DEG C；
It is described heating reaction time be 1~for 24 hours.
9. preparation method according to claim 1, which is characterized in that after the heating reaction, filtering, distillation filtrate is obtained
To benzene oxycarboxylic acid ester type compound shown in formula (III).
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045605A (en) * | 2014-07-08 | 2014-09-17 | 贵州大学 | Phenoxymethyl sulfone derivatives as well as synthesis method and application of phenoxymethyl sulfone derivatives |
| CN106831437A (en) * | 2016-02-03 | 2017-06-13 | 华中师范大学 | Ester type compound containing nitroethenyl group and its preparation method and application |
-
2018
- 2018-03-19 CN CN201810226626.2A patent/CN108947826A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045605A (en) * | 2014-07-08 | 2014-09-17 | 贵州大学 | Phenoxymethyl sulfone derivatives as well as synthesis method and application of phenoxymethyl sulfone derivatives |
| CN106831437A (en) * | 2016-02-03 | 2017-06-13 | 华中师范大学 | Ester type compound containing nitroethenyl group and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| WANG, XUEKUN等: "Synthesis and biological evaluation of phenoxyacetic acid derivatives as novel free fatty acid receptor 1 agonists", 《BIOORGANIC & MEDICINAL CHEMISTRY》 * |
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