CN110483320A - A method of double-Oxoacetic Acid esters compound is synthesized using alcohols solvent - Google Patents
A method of double-Oxoacetic Acid esters compound is synthesized using alcohols solvent Download PDFInfo
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Abstract
The present invention relates to a kind of synthetic methods of double-Oxoacetic Acid esters compound, synthesis technology is by diamine, alcohols solvent, oxalate diester anabolic reaction system, nucleophilic substitution occurs and generates the compound containing double-oxoacetate ester, double-Oxoacetic Acid ester compounds are detached from by purification, it is recycled after alcohols solvent recycling, directly participates in reaction process next time.Present invention improves over synthesizing formulas, carry out reaction system in environmental-friendly, easy to industrialized production solvent；The alcohols solvent is easily recycled, and can be recycled for multiple times, and does not need additionally to add solvent, does not also generate additional by-product, and production cost reduces；Without using the relatively hazardous solvent such as tetrahydrofuran, 90% or more reaction yield.The alcohols solvent is easily recycled, and can be recycled for multiple times, and does not need additionally to add solvent, does not also generate additional by-product, and production cost reduces；Without using the relatively hazardous solvent such as tetrahydrofuran, 90% or more reaction yield.
Description
Technical field
The invention belongs to chemosynthesis technical fields, in particular to a kind of to synthesize double-oxoacetate ester using alcohols solvent
The method of class compound.
Background technique
Double-Oxoacetic Acid esters compound is a kind of important chemical synthesis intermediate.
Chinese patent application CN102686643A describes a kind of poly bis oxamides material, it be a kind of bulk strength it is high,
The big elastomeric material of elongation at break.In the step of preparing the material, a kind of similar this patent formula IV structure is provided
The synthetic method of intermediate, specifically by diamine, tetrahydrofuran, diethy-aceto oxalate anabolic reaction system, react generation
Compound containing double-oxoacetate ester.
Chinese patent application CN106750251A, which describes one kind, has interpenetrating networks containing polyether amide block copolymer
The new material of structure.A kind of similar this patent formula IV structure is provided in the preparation step of polyether amide block copolymer
The synthetic method of intermediate is specifically in a reservoir formed containing excess diethyl oxalate, aliphatic diamine, tetrahydrofuran
Reaction system reacts and generates the compound containing double-oxoacetate ester.
Chinese patent application CN107189049A describes a kind of hydridization type polyester and preparation method thereof.In wherein providing
Between product B have chemical structure similar with this patent formula IV.The side of synthesis intermediate product B is provided in corresponding embodiment
Case, specifically reaction system of the composition containing ethanedioic acid second diester, diamine, tetrahydrofuran, react and synthesize intermediate production
Object B.
Tetrahydrofuran is a kind of virose organic solvent of tool, be likely to occur after high concentration sucking dizzy, headache, it is uncomfortable in chest,
The symptoms such as pectoralgia, cough, out of strength, stomachache, dry, Nausea and vomiting, to skin, eyes, the irritating symptom of respiratory system.To people
Body liver function, sexual function, fecundity, renal function etc. are harmful, while to aquatile nocuousness, may generate to water body environment
Long-term adverse effect.This is unfavorable for industrialized production and the health of operator.
For these reasons, the present invention is specifically proposed.
Summary of the invention
Double-oxo second is synthesized using alcohols solvent it is an object of the invention to overcome the deficiencies of the prior art and provide a kind of
The method of acid esters compound, the technical problem to be solved is that by optimizing reaction system, make reaction it is environmental-friendly, be easy to
It is carried out in the solvent of industrialized production, and the alcohols solvent can be recycled for multiple times, double-Oxoacetic Acid esters compound yield
90% or more.
The purpose of the present invention and the technical problem to be solved is that be achieved through the following technical solutions.
A method of double-Oxoacetic Acid esters compound, synthesis technology are synthesized using alcohols solvent are as follows:
(1) diamine is dissolved in alcohols solvent, forms homogeneous solution, the homogeneous solution is slowly added into oxalic acid
In diester, the reaction system containing diamine, alcohols solvent, oxalate diester is formed, carries out nucleophilic substitution at room temperature；
(2) purification is carried out to the product of step (1) and is detached from acquisition pair-Oxoacetic Acid esters compound, alcohols solvent recycling
After be recycled, directly participate in reaction process next time.Reaction process is as follows:
Wherein RaIt is the alkyl of 2-40 carbon atom, R1It is the alkyl of 1-40 carbon atom.
Formula I is diamine, and formula II is oxalate diester, and formula III is alcohols solvent, and formula IV is the chemical combination of double-oxoacetate ester
Object.
The alcohols solvent be and fatty alcohol corresponding to alkoxy in the oxalate diester.
Specifically, the alkoxy in the oxalate diester and corresponding fatty alcohol include but is not limited to methoxyl group and first
Alcohol, ethyoxyl and ethyl alcohol, propoxyl group and normal propyl alcohol, isopropoxy and isopropanol, butoxy and n-butanol, isobutoxy and isobutyl
Alcohol, tert-butoxy and the tert-butyl alcohol.
Specifically, the source of the fatty alcohol is new purchase fatty alcohol, or the fat for batch reuse before same reaction system
Alcohol, or the mixture for the two.
Specifically, the homogeneous solution that the diamine and the alcohols solvent are formed, concentration are 0.01~1g/mL.
Specifically, the molar ratio of the diamine and the oxalate diester is 1:4~50.
The beneficial effects of the present invention are: the use of (1) by alcohols solvent, make reaction system it is environmental-friendly, be easy to work
It is carried out in the solvent that industry metaplasia produces；(2) alcohols solvent is easily recycled, and can be recycled for multiple times, and does not need additionally to add molten
Agent, does not generate additional by-product yet, and production cost reduces；(3) 90% or more reaction yield.
Detailed description of the invention
Fig. 1 is the reaction route circulation schematic diagram that double-Oxoacetic Acid esters compound is synthesized using alcohols solvent；
Fig. 2 is the first time obtained with this patent fatty alcohol and reuse fatty alcohol respectively as solvent, anabolic reaction system
Synthetic product and second of synthetic product, ((6- ((ethyoxyl (oxo) acetyl group) amino) hexyl) amino) (oxo) acetic acid second
The FTIR spectrum of ester (1) and (2) and its raw material；
Fig. 3 is to make solvent with this patent fatty alcohol, the first time synthetic product that anabolic reaction system obtains, ((6- ((ethoxy
Base (oxo) acetyl group) amino) hexyl) amino) (oxo) ethyl acetate (1)1H-NMR spectrum (CDCl3-d1)；
Fig. 4 is to use reuse fatty alcohol as solvent, second of synthetic product that anabolic reaction system obtains, ((6- ((ethoxy
Base (oxo) acetyl group) amino) hexyl) amino) (oxo) ethyl acetate (2)1H-NMR spectrum (CDCl3-d1)。
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Comparative example
116g (1mol) 1,6- hexamethylene diamine is dissolved into 500mL tetrahydrofuran, homogeneous solution is formed, then by the solution
It is added drop-wise in 10 times of excessive diethy-aceto oxalates (1460g, 10mol), composition contains 1,6- hexamethylene diamine, tetrahydrofuran, oxalic acid two
The reaction system of ethyl ester under conditions of being stirred at room temperature, occurs nucleophilic substitution and generates ((6- ((ethyoxyl (oxo) acetyl
Base) amino) hexyl) amino) (oxo) ethyl acetate, yield 80%.
Embodiment 1
116g (1mol) 1,6- hexamethylene diamine is dissolved into 400mL ethyl alcohol, homogeneous solution is formed, then the solution is added dropwise
Into 10 times of excessive diethy-aceto oxalates (1460g, 10mol), composition contain 1,6- hexamethylene diamine, ethyl alcohol, diethy-aceto oxalate it is anti-
System is answered, under conditions of being stirred at room temperature, nucleophilic substitution occurs and generates ((6- ((ethyoxyl (oxo) acetyl group) amino)
Hexyl) amino) (oxo) ethyl acetate (1), yield 96%.
By refining spearation reaction product, the mixture of ethyl alcohol and excess diethyl oxalate is obtained.Using Rotary Evaporators,
The mixture is separated at 65~78 DEG C, wherein ethyl alcohol recycling 490ml (rate of recovery 95%), diethy-aceto oxalate recycles 1125g (recycling
Rate 96.3%).
It takes 116g (1mol) 1,6- hexamethylene diamine to be dissolved into 400mL recycling ethyl alcohol again, forms homogeneous solution, then should
Solution is added drop-wise in 8 times of excessive recycling diethy-aceto oxalates (1125g, 7.7mol), and composition contains 1,6- hexamethylene diamine, second again
The reaction system of alcohol, diethy-aceto oxalate under conditions of being stirred at room temperature, occurs nucleophilic substitution and generates ((6- ((ethyoxyl
(oxo) acetyl group) amino) hexyl) amino) (oxo) ethyl acetate (2), yield 93%.
By refining spearation reaction product, the mixture of ethyl alcohol and excess diethyl oxalate is obtained.Using Rotary Evaporators,
The mixture is separated at 65~78 DEG C, wherein ethyl alcohol recycling 500ml (rate of recovery 96.8%), diethy-aceto oxalate recycles 783g and (returns
Yield 94%), continue reuse, participates in reaction process next time.
Fig. 2 is the product synthesized with ethyl alcohol and recycling ethyl alcohol respectively as solvent, ((6- ((ethyoxyl (oxo) acetyl group)
Amino) hexyl) amino) and (oxo) ethyl acetate (1) and (2) FTIR spectrum；Fig. 3 is the product synthesized with ethanol as solvent,
((6- ((ethyoxyl (oxo) acetyl group) amino) hexyl) amino) (oxo) ethyl acetate (1)1H-NMR spectrum (CDCl3-
d1)；Fig. 4 is with the product of recycling ethanol as solvent synthesis, ((6- ((ethyoxyl (oxo) acetyl group) amino) hexyl) amino)
(oxo) ethyl acetate (2)1H-NMR spectrum (CDCl3-d1)。
Embodiment 2
60g (1mol) 1,2- ethylenediamine is dissolved into 300mL methanol, homogeneous solution is formed, then the solution is added dropwise
Into 7 times of excessive dimethyl oxalates (826.2g, 7mol), composition contains the reaction of 1,2- ethylenediamine, methanol, dimethyl oxalate
System under conditions of being stirred at room temperature, occurs nucleophilic substitution and generates ((2- ((methoxyl group (oxo) acetyl group) amino) second
Base) amino) (oxo) methyl acetate (1), yield 91%.
By refining spearation reaction product, the mixture of methanol and excessive dimethyl oxalate is obtained.It is set using vacuum distillation
It is standby, the mixture is separated at 50~64 DEG C, wherein Methanol Recovery 350ml (rate of recovery 92%), dimethyl oxalate recycles 561g and (returns
Yield 95%).
It takes 60g (1mol) 1,2- ethylenediamine to be dissolved into 300mL recycling methanol again, forms homogeneous solution, then should
Solution is added drop-wise in 7 times of excessive dimethyl oxalates (826.2g, 7mol), and wherein 561g is recycling dimethyl oxalate, again group
At the reaction system for containing 1,2- ethylenediamine, methanol, dimethyl oxalate, under conditions of being stirred at room temperature, it is anti-that nucleophilic displacement of fluorine occurs
((2- ((methoxyl group (oxo) acetyl group) amino) ethyl) amino) (oxo) methyl acetate (2), yield 95% should be generated.
By refining spearation reaction product, the mixture of methanol and excessive dimethyl oxalate is obtained.It is set using vacuum distillation
It is standby, the mixture is separated at 50~64 DEG C, wherein Methanol Recovery 344ml (rate of recovery 90%), dimethyl oxalate recycles 539g and (returns
Yield 91%), continue reuse, participates in reaction process next time.
Embodiment 3
74g (1mol) 1,3- propane diamine is dissolved into 500mL n-butanol, homogeneous solution is formed, then drips the solution
It is added in 12 times of excessive dibutyl oxalates (2425.4g, 12mol), composition contains 1,3- propane diamine, n-butanol, two fourth of oxalic acid
The reaction system of ester under conditions of being stirred at room temperature, occurs nucleophilic substitution and generates ((3- ((butoxy (oxo) acetyl group)
Amino) propyl) amino) (oxo) butyl acetate (1), yield 92%.
By refining spearation reaction product, the mixture of n-butanol and excessive dibutyl oxalate is obtained.Use vacuum distillation
Equipment separates the mixture at 100~117 DEG C, wherein n-butanol recycling 611ml (rate of recovery 89.5%), and dibutyl oxalate returns
It receives 1997g (rate of recovery 99%).
It takes 74g (1mol) 1,3- propane diamine to be dissolved into 500mL recycling n-butanol again, forms homogeneous solution, then will
The solution is added drop-wise in 10 times of excessive recycling dibutyl oxalates (1997g, 9.9mol), again composition contain 1,3- propane diamine,
The reaction system of n-butanol, dibutyl oxalate under conditions of being stirred at room temperature, occurs nucleophilic substitution and generates ((3- ((fourth oxygen
Base (oxo) acetyl group) amino) propyl) amino) (oxo) butyl acetate (2), yield 90%.
By refining spearation reaction product, the mixture of n-butanol and excessive dibutyl oxalate is obtained.Use vacuum distillation
Equipment separates the mixture at 100~117 DEG C, wherein n-butanol recycling 623ml (rate of recovery 91%), dibutyl oxalate recycling
1589g (rate of recovery 98%).Continue reuse, participates in reaction process next time.
Experimental result is as follows:
The results showed that by using method of the invention, 90% or more reaction yield.
Claims (7)
1. a kind of method for synthesizing double-Oxoacetic Acid esters compound using alcohols solvent, it is characterised in that include the following steps,
Diamine is dissolved in alcohols solvent, homogeneous solution is formed, the homogeneous solution is slowly added into oxalate diester,
Nucleophilic substitution is carried out at room temperature；
Purification is carried out to the product of step (1) and is detached from acquisition pair-Oxoacetic Acid esters compound, recycling after alcohols solvent recycling makes
With directly participating in reaction process next time；
The alcohols solvent be and fatty alcohol corresponding to alkoxy in the oxalate diester.
2. the method as described in claim 1, which is characterized in that the structure of the oxalate diester is shown in formula I,
Formulas I:
The structure of the alcohols solvent as shown in Formula II,
Formula II:
R1-OH；
Wherein R1For the alkyl of 1-40 carbon atom.
3. method according to claim 2, which is characterized in that alkoxy and corresponding fatty alcohol packet in the oxalate diester
Include but be not limited to methoxyl group and methanol, ethyoxyl and ethyl alcohol, propoxyl group and normal propyl alcohol, isopropoxy and isopropanol, butoxy
With n-butanol, isobutoxy and isobutanol, tert-butoxy and the tert-butyl alcohol.
4. the method as described in claim 1, which is characterized in that the structure of the diamine as shown in formula III,
Formula III:
Wherein RaFor the alkyl of 2-40 carbon atom.
5. the method as described in claim 1, which is characterized in that the double-Oxoacetic Acid esters compound structure such as formula IV institute
Show,
Formula IV:
Wherein R1For the alkyl of 1-40 carbon atom, RaFor the alkyl of 2-40 carbon atom.
6. the method as described in claim 1, which is characterized in that the homogeneous that the diamine and the alcohols solvent are formed
The concentration of solution is 0.01~1g/mL.
7. the method as described in claim 1, which is characterized in that the molar ratio of the diamine and the oxalate diester is 1:4
~50.
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| CN109161015A (en) * | 2018-07-26 | 2019-01-08 | 东华大学 | A kind of high heat resistance alternating copolymerization amide resin and preparation method thereof |
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2019
- 2019-09-10 CN CN201910851012.8A patent/CN110483320A/en active Pending
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| CN102712758A (en) * | 2009-12-30 | 2012-10-03 | 3M创新有限公司 | Methods of making polydiorganosiloxane polyoxamide copolymers |
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Application publication date: 20191122 |