CN106278914B - A kind of synthesis technique of increase production of amines - Google Patents
A kind of synthesis technique of increase production of amines Download PDFInfo
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- CN106278914B CN106278914B CN201610689161.5A CN201610689161A CN106278914B CN 106278914 B CN106278914 B CN 106278914B CN 201610689161 A CN201610689161 A CN 201610689161A CN 106278914 B CN106278914 B CN 106278914B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
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Abstract
The invention discloses a kind of synthesis technique of increase production of amines, belong to technical field of fine.The technique comprises the following steps：A. by 3, after 4 chlorophenesic acids and alkali metal hydroxide are dissolved in polar aprotic solvent, add 1,2 dihalo- ethane, after heating, 0.5~1h of insulation reflux, rectifying, unreacted 1,2 dihalo- ethane and segment polarity non-protonic solvent are recycled, bottom is intermediate product and the mixed liquor of polar aprotic solvent；B. diethylamine is added in the intermediate product and the mixed liquor of polar aprotic solvent that are obtained into step A, after being heated to reflux 8~10h, add alkali metal hydroxide, stirring, then filters, will obtain increase production of amines after filtrate rectifying, the present invention is homogeneous reaction by varying traditional heterogeneous reaction, while reducing cost, suppress the generation of side reaction, improve the yield of product.
Description
Technical field
The present invention relates to a kind of preparation process of increase production of amines, belong to technical field of fine.
Background technology
Increase production of amines, chemical name 2-（3,4- Dichlorophenoxies）Alcohol, is that Yokoyama in 1977 etc. has found and by U.S.
A kind of new plant growth regulator of Stauffer companies of state exploitation.By promoting, increasing or suppress, reduce endogenous plant
The level of hormone, can effectively adjust the growth and development of plant.For soybean, corn, wheat, cotton, beet, ginseng guayule rubber and
The crops such as various vegetables have different degrees of effect of increasing production.The disease-resistant of plant can be strengthened with Multiple Pesticides fertilizer compounding use
Ability, improves bactericidal effect.Increase production of amines is agriculturally being used widely with its unique multi-function action.
Mainly there are amination method, alkylation-amination by the synthetic method that starting material prepares increase production of amines of 3,4- chlorophenesic acids
5 kinds of methods such as method, reduction of amide method, ethylene oxide open loop-sulfonyl method of substitution and sulfonyl substitution improved method.Existing method
In, when preparing intermediate 2 through alkylation with 3,4- chlorophenesic acids, using heterogeneous reaction, in water and 1,2- dihalo-s ethane and
In the presence of phase transfer catalyst, more than back flow reaction 10h just can obtain intermediate 2, and with the generation of two substitution products.
In addition, in alkaline conditions, with the increase in reaction time, 1,2- dihalo- ethane occurs elimination reaction generation alkenyl halide and overflows
System so that the dosage of solvent greatly increases.In existing method, it is also using non-to prepare object 3 through amination method with intermediate 2
Homogeneous reaction, under the conditions of existing for lye, solvent and phase transfer catalyst, reacts more than 15h with diethylamine, obtains object
Increase production of amines, and yield is not high.
The structural formula of foregoing intermediate 2 is：
The structural formula of object 3 is：
Synthetic method of the prior art such as Qiu Jun, Du Baolin, Wang Kun, Wang Jinjun, 2- (3 ', 4 '-dichlorophenoxy)
The synthetic method of alcohol, chemistry world, is mentioned in periodical disclosed in the 10th phase：Volume increase is prepared with heterogeneous method
Amine, it is specific as follows：
1）1.64 g 3,4- chlorophenesic acids, 20 mL dichloroethanes, 0.08 g are added in 100 mL four-hole boiling flasks
Tetrabutylammonium bromide, the 20mL aqueous solutions of the potassium hydroxide containing 2.80g.10h is stirred at reflux, is cooled to room temperature, it is organic to separate lower floor
Thing, water layer extract (2 × 10 mL) with 1,2- dichloroethanes, merge extracting solution, are dried, steamed with anhydrous magnesium sulfate after washing
Dichloroethanes.For Liquid Residue through silica gel column chromatography, hexamethylene elution, 2.10g thick liquids, yield 94.1% are obtained after sloughing solvent；
2）2.10g l- chloro- 2- (3 ', 4 '-dichlorophenoxy) ethane is added in the three-necked flask of 50 mL,
1.40g potassium hydroxide, 1.5 mL water, 0.35 g tetrabutylammonium bromide and 1.70g diethylamine, are heated to 85 DEG C under stirring,
React 15h.It is cooled to room temperature, adds 5mL water.Organic layer is separated, water layer is washed with toluene (2 × 10 mL), merges extraction
Liquid.With the salt acid elution of 10% (mass fraction), it is 9~10 to be neutralized to pH with the sodium hydroxide of 10% (mass fraction) afterwards, analysis
Go out grease extracted by ether, anhydrous magnesium sulfate drying, 2.05g, yield 84.0% are obtained after sloughing solvent.
Such scheme belongs to heterogeneous reaction, and the reaction time is longer, and solvent-oil ratio is big, and yield is low, post-processing operation
It is complicated.
And for example Zhang Tianlin, DCPTA new synthetic method, Qingtao Chemical Engineering College's journal, carries in the periodical disclosed in the 3rd phase of volume 15
Arrive：Increase production of amines is prepared with heterogeneous method, it is specific as follows：
L) 16.3g (0.10 mol) 3,4- chlorophenesic acids and 4g sodium hydroxides are weighed in autoclave, add 50mL go from
Sub- water, heats 80~90 DEG C of reaction 2h, 3,4- chlorophenesic acid sodium-salt aqueous solutions is made.
2) treat that the 3.4- chlorophenesic acid sodium-salt aqueous solutions in autoclave are cooled to room temperature, add 40mL 1,2- dichloroethanes
With 0.2g tetrabutylammonium bromide, 90~95 DEG C of reaction 15h are heated to.After reaction, stand and separate organic layer.Distilled after drying
Excessive 1,2- dichloroethanes is recycled, intermediate 2- (3,4- dichlorophenoxy) chloroethanes can be obtained.
3) by intermediate above and 30mL diethylamine, 50mL benzene, puts into autoclave, is heated to 120 DEG C of reaction 6h.Instead
After answering, excessive diethylamine and solvent is recovered by distillation, DCPTA salt acid crystals can be separated out after cooling.Through ethanol weight
Crystallization purifying, can obtain DCPTA hydrochloride 24.8g, yield 89.7% (with 3,4- chlorophenesic acids meter).
Such scheme carries out heterogeneous reaction with autoclave, and reaction time length, is carried by the natural pressure of System forming
High reaction temperature, it is higher to equipment requirement, it is unfavorable for industrialized production.
The content of the invention
Present invention seek to address that the problem of preparation time of increase production of amines is long in the prior art, yield is low, of high cost, there is provided one
The new technique for synthesizing of kind increase production of amines, substitutes heterogeneous reaction of the prior art, without adding phase transfer catalysis (PTC) with homogeneous reaction
Agent, has the advantages of generated time is short, and cost is low, final product high income.
In order to realize foregoing invention purpose, technical scheme is as follows：
A kind of synthesis technique of increase production of amines, it is characterised in that：Comprise the following steps：
A. after 3,4- chlorophenesic acids and alkali metal hydroxide being dissolved in polar aprotic solvent, 1,2- dihalo-s are added
Ethane, after heating, insulation 0.5~1h of reflux, rectifying, it is molten to recycle unreacted 1,2- dihalo-s ethane and segment polarity aprotic
Agent, bottom are intermediate product and the mixed liquor of polar aprotic solvent；
B. the intermediate product and the mixed liquor of polar aprotic solvent obtained into step A adds diethylamine, heats back
After flowing 8~10h, alkali metal hydroxide is added, is stirred, is then filtered, increase production of amines will be obtained after filtrate rectifying；
The alkali metal hydroxide is potassium hydroxide, one kind in sodium hydroxide.
The reaction process of step A is as follows：
The reaction process of step B is as follows：
Further, the highly polar non-protonic solvent is one kind in DMF, DMSO, NMP, DMAC.
In step A, 1, the 2- dihalo-s ethane is 1,2- dichloroethanes, one kind in 1,2- Bromofumes.
In step A, the dosage of the alkali metal hydroxide is 3.5~4 times of the amount of the material of 3,4- chlorophenesic acids.
In step A, the dosage of the highly polar non-protonic solvent is 4~6 times of the amount of the material of 3,4- chlorophenesic acids.
In step A, the dosage of 1, the 2- dihalo-s ethane is 8~10 times of the amount of the material of 3,4- chlorophenesic acids.
In step B, the ratio between amount of material of alkali metal hydroxide and 3, the 4- chlorophenesic acid is 1:1.
In step A, the temperature being heated to reflux is 75~85 DEG C.
In step B, the temperature being heated to reflux is 75~90 DEG C.
In step A and step B, after filtering, filtrate and filter residue are obtained；Filter residue is washed with solvent, obtains cleaning solution, then will filter
Rectifying again after liquid and cleaning solution merge, to further improve product yield.
Beneficial effects of the present invention：
（1）In the prior art, the preparation of increase production of amines is heterogeneous reaction, i.e., phenol potassium or sodium phenolate is formed in water phase, so
After add phase transfer catalyst, then reacted with 1,2- dihalo-s ethane.The present invention is according to 1,2- dihalo-s ethane and polar aprotic
Solvent dissolves each other, and potassium hydroxide/sodium has the principle of certain solubility in highly polar non-protonic solvent, make potassium hydroxide/
Sodium and 3,4- chlorophenesic acid are initially formed phenol potassium/sodium salt in the medium of this highly polar non-protonic solvent, then with 1,2- bis-
Halogen ethane composition it is homogeneous in further occur substitution reaction.It is achieved thereby that homogeneous reaction.
After the step A of the present invention uses homogeneous reaction, compared with prior art, without adding phase transfer catalyst, alkali gold
The dosage for belonging to hydroxide is also reduced therewith, and the reaction time greatly shortens, shortening and alkali metal hydrogen-oxygen with the reaction time
The reduction of compound dosage, the elimination reaction of 1,2- dihalo- ethane are significantly suppressed, and solvent recovering rate is improved, and is dropped significantly
Low production cost；
After step B of the present invention uses homogeneous reaction, compared with prior art, when reaction need not add phase transfer catalyst and
Alkali metal hydroxide, diethylamine not only as reactant but also served as the effect of acid binding agent, and simplified operation.Reaction is completed
Afterwards, adding alkali metal hydroxide can also avoid intermediate product that elimination reaction occurs under strongly alkaline conditions, so as to effectively press down
The generation of side reaction has been made, has improved the yield of reaction conversion ratio and product.
（2）Polar aprotic solvent in the present invention is one kind in DMF, DMSO, NMP, DMAC, the polarity of the solvent
Greatly, there is certain dissolubility to phenol potassium/sodium, its boiling point is high, can improve reaction reflux temperature after being mixed with 1,2- dihalo-s ethane, add
Fast response speed.
（3）In the present invention in step A, the dosage of alkali metal hydroxide is the 3.5 of the amount of the material of 3,4- chlorophenesic acids
~4 times, dosage has been reduced when the dosage of alkali metal hydroxide is compared with heterogeneous reaction, while reducing cost, makes solvent 1,
The elimination reaction of 2- dihalo- ethane is also significantly suppressed.
（4）In step A of the present invention, the dosage of the highly polar non-protonic solvent is the amount of the material of 3,4- chlorophenesic acids
4~6 times；The dosage of 1,2- dihalo- ethane is 8~10 times of the amount of the material of 3,4- chlorophenesic acids, 1,2- dihalo- ethane mistake
Amount can avoid the generation of two substitution accessory substances；Test of many times proves that highly polar non-protonic solvent and 1,2- dihalo- ethane is preceding
In the case of stating usage amount, the equal phase effect of system is good, and reaction effect is good.
Embodiment
The present invention is described in further detail with reference to embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1
A kind of synthesis technique of increase production of amines, comprises the following steps：
A. after 3,4- chlorophenesic acids and alkali metal hydroxide being dissolved in polar aprotic solvent, 1,2- dihalo-s are added
Ethane, after heating, insulation reflux 0.5h, rectifying, recycles unreacted 1,2- dihalo-s ethane and segment polarity non-protonic solvent,
Bottom is intermediate product and the mixed liquor of polar aprotic solvent；
B. diethylamine is added in the intermediate product and the mixed liquor of polar aprotic solvent that are obtained into step A, is heated
Flow back after 8h, add alkali metal hydroxide, stir, then filter, increase production of amines will be obtained after filtrate rectifying；
In above-mentioned steps A and step B, the alkali metal hydroxide is potassium hydroxide.
Embodiment 2
A kind of synthesis technique of increase production of amines, comprises the following steps：
A. after 3,4- chlorophenesic acids and alkali metal hydroxide being dissolved in polar aprotic solvent, 1,2- dihalo-s are added
Ethane, after heating, insulation reflux 1h, rectifying, recycles unreacted 1,2- dihalo-s ethane and segment polarity non-protonic solvent, kettle
Bottom is intermediate product and the mixed liquor of polar aprotic solvent；
B. diethylamine is added in the intermediate product and the mixed liquor of polar aprotic solvent that are obtained into step A, is heated
Flow back after 10h, add alkali metal hydroxide, stir, then filter, increase production of amines will be obtained after filtrate rectifying；
In above-mentioned steps A and step B, the alkali metal hydroxide is sodium hydroxide.
The polar aprotic solvent of the present embodiment is DMF；In step A, 1, the 2- dihalo-s ethane is 1,2-, bis- chloroethenes
Alkane.
Embodiment 3
A kind of synthesis technique of increase production of amines, comprises the following steps：
A. after 3,4- chlorophenesic acids and alkali metal hydroxide being dissolved in polar aprotic solvent, 1,2- dihalo-s are added
Ethane, after heating, insulation reflux 0.5h, rectifying, recycles unreacted 1,2- dihalo-s ethane and segment polarity non-protonic solvent,
Bottom is intermediate product and the mixed liquor of polar aprotic solvent；
B. diethylamine is added in the intermediate product and the mixed liquor of polar aprotic solvent that are obtained into step A, is heated
Flow back after 9h, add alkali metal hydroxide, stir, then filter, increase production of amines will be obtained after filtrate rectifying；
In above-mentioned steps A and step B, the alkali metal hydroxide is sodium hydroxide.
The polar aprotic solvent of the present embodiment is DMAC；In step A, 1, the 2- dihalo-s ethane is 1,2- dibromo second
Alkane；The dosage of alkali metal hydroxide is 3.5 times of the amount of the material of 3,4- chlorophenesic acids；The use of highly polar non-protonic solvent
Measure the amount of the material for 3,4- chlorophenesic acids 4 times.
Embodiment 4
A kind of synthesis technique of increase production of amines, comprises the following steps：
A. after 3,4- chlorophenesic acids and alkali metal hydroxide being dissolved in polar aprotic solvent, 1,2- dihalo-s are added
Ethane, after heating, insulation reflux 1h, rectifying, recycles unreacted 1,2- dihalo-s ethane and segment polarity non-protonic solvent, kettle
Bottom is intermediate product and the mixed liquor of polar aprotic solvent；
B. the intermediate product and the mixed liquor of polar aprotic solvent obtained into step A adds diethylamine, heats back
After flowing 8h, alkali metal hydroxide is added, is stirred, is then filtered, increase production of amines will be obtained after filtrate rectifying；
In above-mentioned steps A and step B, the alkali metal hydroxide is sodium hydroxide.
The polar aprotic solvent of the present embodiment is NMP.
In step A, 1, the 2- dihalo-s ethane is 1,2- Bromofumes；The dosage of alkali metal hydroxide is 3,4- dichloros
4 times of the amount of the material of phenol；The dosage of highly polar non-protonic solvent is 6 times of the amount of the material of 3,4- chlorophenesic acids；1,
The dosage of 2- dihalo- ethane is 8 times of the amount of the material of 3,4- chlorophenesic acids, and 1,2- saturated dihalide can excessively avoid two from taking significantly
For the generation of accessory substance；The temperature being heated to reflux is 75~85 DEG C.
In step B, the ratio between amount of material of alkali metal hydroxide and 3,4- chlorophenesic acid is 1:1；The temperature being heated to reflux
Spend for 75~90 DEG C；In step A and step B, after filtering, filtrate and filter residue are obtained；Filter residue is washed with solvent, obtains cleaning solution, so
Rectifying again after afterwards merging filtrate and cleaning solution, to further improve product yield.
Embodiment 5
A kind of synthesis technique of increase production of amines, comprises the following steps：
A. the 3,4- chlorophenesic acids that purity is 97% are added in the there-necked flask of 1L（67.22g 0.4mol）、KOH
（89.6g 1.6mol）And NMP（237g, 2.4mol）, stirring, after most of KOH dissolvings, adds 1,2- dichloroethanes
（400g,4.04mol）, 75~85 DEG C are heated to, insulation reaction 1h.After stopping heating being cooled to room temperature, filter, obtain filtrate and filter
Slag, then washs filter residue with 20g NMP, merges washing lotion and filtrate, rectifying, recycles unreacted 1,2- dichloroethanes and part
NMP, the nmp solution of bottom 166g intermediate products, is directly used in next step（The LC contents 48.99% of intermediate product, yield are
90.16%）；
B. in the there-necked flask of 500mL, the nmp solution of above-mentioned intermediate product is added（81.32g containing intermediate product,
0.36mol）And diethylamine（78.99g 1.08mol）, 75 DEG C are heated to, starts to flow back.When reflux temperature rises to 90 DEG C, reaction
Finish, stop heating, be cooled to room temperature.Then NaOH is added into reaction bulb（14.4g 0.36mol）, stirring, 0.5h, dissociates
Diethylamine, filters, and obtains filtrate and filter residue, and washs filter residue with 10g NMP, merges washing lotion and filtrate, rectifying, obtains object
Increase production of amines（88.45g, LC content 98%, yield 91.84%）.
The above, is only presently preferred embodiments of the present invention, not does limitation in any form to the present invention, it is every according to
Any simply modification, the equivalent variations made according to the technical spirit of the present invention to above example, each fall within the protection of the present invention
Within the scope of.
Claims (6)
- A kind of 1. synthesis technique of increase production of amines, it is characterised in that：Comprise the following steps：A. after 3,4- chlorophenesic acids and alkali metal hydroxide being dissolved in polar aprotic solvent, 1,2- dihalo- second is added Alkane, after heating, insulation 0.5~1h of reflux, rectifying, it is molten to recycle unreacted 1,2- dihalo-s ethane and segment polarity aprotic Agent, bottom are intermediate product and the mixed liquor of polar aprotic solvent；B. diethylamine is added in the intermediate product and the mixed liquor of polar aprotic solvent that are obtained into step A, is heated to reflux 8 After~10h, alkali metal hydroxide is added, is stirred, is then filtered, increase production of amines will be obtained after filtrate rectifying；The one kind of the alkali metal hydroxide for potassium hydroxide, in sodium hydroxide, the polar aprotic solvent is DMF, One kind in DMSO, NMP, DMAC,In step A, the dosage of alkali metal hydroxide is 3.5~4 times of the amount of the material of 3,4- chlorophenesic acids, aprotic, polar Property solvent dosage be 4~6 times of amount of the material of 3,4- chlorophenesic acids, the dosage of 1,2- dihalo- ethane is 3,4- chlorophenesic acids 8~10 times of amount of material.
- A kind of 2. synthesis technique of increase production of amines as claimed in claim 1, it is characterised in that：In step A, 1, the 2- dihalo-s second Alkane is 1,2- dichloroethanes, one kind in glycol dibromide.
- A kind of 3. synthesis technique of increase production of amines as claimed in claim 1, it is characterised in that：In step B, the alkali metal hydrogen-oxygen The ratio between compound and the amount of material of 3,4- chlorophenesic acids are 1:1.
- A kind of 4. synthesis technique of increase production of amines as claimed in claim 1, it is characterised in that：It is described to be heated to reflux in step A Temperature is 75~85 DEG C.
- A kind of 5. synthesis technique of increase production of amines as claimed in claim 1, it is characterised in that：It is described to be heated to reflux in step B Temperature is 75~90 DEG C.
- A kind of 6. synthesis technique of increase production of amines as claimed in claim 1, it is characterised in that：In step A and step B, after filtering, Obtain filtrate and filter residue；Filter residue is washed with solvent, obtains cleaning solution, rectifying again after then merging filtrate and cleaning solution.
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