CN109928899A - A method of synthesis aldehyde or methyl ketone and sodium hydrogensulfite addition product - Google Patents
A method of synthesis aldehyde or methyl ketone and sodium hydrogensulfite addition product Download PDFInfo
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- CN109928899A CN109928899A CN201711365126.9A CN201711365126A CN109928899A CN 109928899 A CN109928899 A CN 109928899A CN 201711365126 A CN201711365126 A CN 201711365126A CN 109928899 A CN109928899 A CN 109928899A
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- aldehyde
- methyl ketone
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- addition product
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Abstract
A method of synthesis aldehyde or methyl ketone and sodium hydrogensulfite addition product；By aldehyde or methyl ketone and NaHSO3Aqueous solution mixing is reacted, and reaction solution is added in solvent A, upper solution is then demultiplex out, and solvent B is added in upper solution, isolates solid, then sufficiently washed with solvent B, and being finally dried to obtain white powder solid is product；The solvent A and solvent B are polar solvent, and the polarity of the solvent A is less than the polarity of solvent B；The solvent A is necessary for aprotic solvent.Compared with prior art, synthesis technology step of the present invention, process are simple, easily operated, regulation；Synthesis process is high-efficient, and a few minutes just can complete to react；The aldehyde of synthesis or the sodium hydrogensulfite addition product yield of methyl ketone are high, with high purity.
Description
Technical field
The present invention provides a kind of synthesis aldehyde or the methods of methyl ketone and sodium hydrogensulfite addition product.
Background technique
Aldehyde or methyl ketone, which are easy to happen reaction under certain condition with sodium hydrogensulfite and generate corresponding sodium hydrogensulfite, to be added
At reaction mixture, there is certain invertibity due to synthesizing the reaction of its sodium hydrogensulfite addition product from aldehydes or ketones how
High efficiency, high productivity obtain the sodium hydrogensulfite addition product of pure aldehyde or methyl ketone and back reaction are avoided to become
The emphasis and difficult point of research.For can from aldehyde or methyl ketone high yield, high-purity, expeditiously synthesize the sulfurous acid of aldehyde or methyl ketone
Hydrogen sodium addition product, researchers are seeking always new method.
Aldehyde or methyl ketone can be used for identifying, separate or purify related aldehyde ketone to the addition of sodium hydrogensulfite, can also be direct
Synthesize cyanalcohol, the precursor as synthesizing high temperature polymer poly benzimidazole.The addition reaction of aldehyde or methyl ketone and sodium hydrogensulfite
And its addition product all has great importance either to basic research, or to industry application.
Summary of the invention
It is an object of the invention to provide a kind of methods of synthesis aldehyde or methyl ketone sodium hydrogensulfite addition product: in certain temperature
By a certain amount of aldehyde or methyl ketone and a certain amount of NaHSO under degree3Reaction solution, is added to by aqueous solution mixing after a period of time
In the solvent A of certain temperature, upper solution is then demultiplex out, the solvent B of certain volume is added at a certain temperature, isolates solid
Body, then sufficiently washed with solvent B, being finally dried to obtain white powder solid is product.
The solvent A is n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc), N- crassitude
Ketone (NMP), one or more of dimethyl sulfoxide (DMSO).Wherein solvent A is necessary for aprotic solvent, and polarity is small
In the polarity of solvent B.If will be unable to obtain addition product using other class solvents (listed solvent in such as following solvent B), and
Only reactant NaHSO3, so the use of solvent A is very crucial, need to be clear from the order of polarity and aprotic solvent of solvent
Advantage just can be carried out the selection of solvent.
The solvent B is ethyl alcohol, methanol, propyl alcohol, isopropanol, ether, tetrahydrofuran, acetonitrile, acetone, chloroform, dichloromethane
One or more of alkane, 1,1- dichloroethanes.The selection of solvent B should polarity it is larger, make its insoluble product again, from
And product is enable to be precipitated from the solution of A, solid product is obtained, finally also wants volatility good, is easy drying.
The quality and NaHSO of the aldehyde or methyl ketone3Mass ratio be 1:1.5~1:3；
The NaHSO3Quality and water volume ratio be 0.5:1~0.1:1g/mL；
The volume ratio of the quality and solvent A of the aldehyde or methyl ketone is 1:14~1:40g/mL；
The volume of the solvent A and the volume ratio of solvent B are 2:1~1:10；
Ratio between above-mentioned reactant and solvent should be moderate, and the yield and purity for otherwise obtaining product can all reduce.
The separation method is one or more of centrifugation, natural filtration, vacuum filter, filters pressing；These types behaviour
It can guarantee that product is quickly separated with solvent, back reaction rate is small, and yield and the purity for obtaining product are higher.
The temperature being added in solvent A is 0~20 DEG C；The temperature being added in solvent B is 0~30 DEG C.It is molten
The temperature of agent A and solvent B should keep lower, will be unable to obtain product beyond temperature range.
The drying means is forced air drying or vacuum drying；The drying temperature is room temperature~100 DEG C；When described dry
Between be 2~48h.Drying temperature is lower will to make drying time long, and products collection efficiency is low；If drying temperature is more than 100 DEG C, obtain
Solid is NaHSO3And it is unable to get product.
It is described to use solvent B mode of washing as 30~45 DEG C of heating after washing 6 times above or addition solvent B are repeatedly added and stir
Mix be repeated 3 times it is above.Multiplicating washing, which just can guarantee, completely removes solvent A, obtains pure product.
The aldehyde or methyl ketone and NaHSO3The order by merging of aqueous solution can be aldehyde or methyl ketone is added to NaHSO3It is water-soluble
Liquid is also possible to NaHSO3Aqueous solution is added to aldehyde or methyl ketone；
The aldehyde or methyl ketone and NaHSO3Reactant aqueous solution temperature is 0~80 DEG C；The reaction time is 5~60min；
The aldehyde of synthesis or the structural formula of methyl ketone sodium hydrogensulfite addition product are as follows:
Wherein R1=H or CH3；R2The straight chained alkyl or C3-C18 branched alkyl or phenyl of=H or C1-C18 orThe wherein straight chained alkyl of R=H or C1-C6 or C3-C8 branched alkyl.
The synthesis of aldehyde of the present invention or the sodium hydrogensulfite addition product of methyl ketone has the advantages that
(1) synthesis technology step, process are simple, easily operated, regulation；
(2) synthesis process is high-efficient, and a few minutes just can complete to react；
(3) aldehyde synthesized or the sodium hydrogensulfite addition product yield of methyl ketone are high, with high purity.
Detailed description of the invention
Fig. 1 is Fourier's infrared spectrum of aldehyde or the sodium hydrogensulfite addition product of methyl ketone in embodiment 1.
Fig. 2 is the nucleus magnetic hydrogen spectrum of aldehyde or the sodium hydrogensulfite addition product of methyl ketone in embodiment 1.
Fig. 3 is the nucleus magnetic hydrogen spectrum of substance obtained in comparative example 1.
Fig. 4 is the nucleus magnetic hydrogen spectrum of white solid powder in comparative example 4.
Fig. 5 is the nucleus magnetic hydrogen spectrum for the white crystal that vacuum drying chamber door generates in comparative example 4.
Specific embodiment
Embodiment 1
By 0.5g NaHSO3It is dissolved in 0.8mL deionized water, 0.3g m-terephthal aldehyde, room temperature is then added thereto
Lower concussion obtains light yellow clear solution.It places reaction liquid into ice-water bath, 5mL DMAc is added thereto.It is molten to filter to take supernatant
Liquid is directly added into 10mL methanol, and white solid is obtained after suction filtration, and then stirring 10min is filtered in methyl alcohol, washes repeatedly 8 times,
Drying at room temperature 12h under vacuum conditions after filtering, obtains white powder, yield 67%, purity 93%.It is red using Fourier
Qualitative analysis is carried out to the structure of the addition product of the sodium hydrogensulfite of above-mentioned m-terephthal aldehyde, chemical composition outside.When experiment, with
KBr is background, and a small amount of sample to be tested is taken to be scattered in dry KBr, carries out infrared test using transmission mode.Fig. 1 isophthalic two
The infrared spectrum of the addition product of the sodium hydrogensulfite of formaldehyde.By Figure 114 20,1320,1200,1060,1020 and 700cm-1It is special
Sign peak position can judge the type of functional group in product, carry out qualitative point to the addition product of the sodium hydrogensulfite of m-terephthal aldehyde
Analysis.
Using Bruker ACIII 400 to the structure of the addition product of the sodium hydrogensulfite of above-mentioned m-terephthal aldehyde and pure
Degree carries out qualitative and quantitative analysis, resonant frequency 400.13MHz.When experiment, a small amount of sample to be tested is taken to be dissolved in deuterated two
In methyl sulfoxide, in acquisition sample in Nuclear Magnetic Resonance1H NMR spectra, using tetramethylsilane (TMS) as internal standard.Fig. 2 is
The addition product of m-terephthal aldehyde sodium hydrogensulfite1H NMR.By in Fig. 21Characteristic peak in H NMR at 5.0ppm and 6.0ppm
Position and hydrogen peak area ratio can be seen that the successful synthesis of the sodium hydrogensulfite addition product of m-terephthal aldehyde.In Fig. 21H NMR
Characteristic peak positions and hydrogen peak area ratio at middle 5.0ppm or 6.0ppm and 10ppm can calculate isophthalic two in the present embodiment
The purity of the sodium hydrogensulfite addition product of formaldehyde is 95%.
The sodium hydrogensulfite addition product of m-terephthal aldehyde can be used as preparation high temperature membrane and often use polyphosphazene polymer benzimidazole
(PBI) monomer, and needed in PBI preparation process using aprotic polar solvent (such as DMAc, DMF, NMP or DMSO) as anti-
Solvent is answered, so we demonstrate the sodium hydrogensulfite addition product of m-terephthal aldehyde in common aprotic solvent in the present invention
In dissolubility.
The following table 1 is dissolubility of the sodium hydrogensulfite addition product of m-terephthal aldehyde in common aprotic solvent.
| DMSO | Quickly dissolution at room temperature |
| DMAc | (60 DEG C) dissolution > 4h under high temperature |
| DMF | Dissolution > 1h at room temperature |
| NMP | (60 DEG C) dissolution > 4h under high temperature |
According to dissolubility test case, in PBI preparation process, it can choose the good DMSO of dissolubility and carried out as solvent
Polycondensation reaction prepares PBI.
Comparative example 1
By 4.5g NaHSO3It is dissolved in 15mL deionized water, while 2.9g m-terephthal aldehyde is added, react at room temperature
After 20min, reaction solution is poured into 200mL methanol, has a large amount of white solids to generate so that cannot stir, it is dry after to its into
Row1H NMR characterization.In Fig. 31Characteristic peak positions and hydrogen peak area ratio in H NMR at 5.0ppm or 6.0ppm and 10ppm can be with
The purity for calculating the sodium hydrogensulfite addition product of m-terephthal aldehyde in the comparative example is 30%, shows there is big content of starting materials isophthalic
Dicarbaldehyde is remaining, and has a large amount of white solid NaHSO when being dissolved using deuterated DMSO3Residue gives m-terephthal aldehyde
Sodium hydrogensulfite addition product purification and the later period recycle create great difficulties comparative example 2
By 0.9g NaHSO3It is dissolved in 2mL deionized water, 0.5g m-terephthal aldehyde is then added, after reacting 20min.
Under the conditions of 30 DEG C, above-mentioned reaction solution will be added in DMF solution while stirring, and there are a large amount of white solids after reacting 2min
It generates.Similarly,1H NMR characterization result shows the purity of the sodium hydrogensulfite addition product of m-terephthal aldehyde in comparative example 3 only
It is 30% or so, and there are a large amount of solid NaHSO3Insoluble in DMSO.
Comparative example 3
By 0.9g NaHSO3It is dissolved in 2mL deionized water, while 50 DEG C of reaction 15min of 0.5g m-terephthal aldehyde is added
Afterwards under the conditions of ice-water bath (5 DEG C), above-mentioned reaction solution is added in 12mL DMF solution while stirring, by solution centrifuging and taking
Then 50mL ethyl alcohol is added in upper layer clear solution under the conditions of ice-water bath into solution, obtain white slurries, is centrifuged Hou Qu lower layer
White solid is centrifuged after being washed with ethyl alcohol, repeated washing operation 7 times, then under vacuum condition, 120 DEG C of dry 2h.Vacuum oven
Door has white crystal appearance.Using1H NMR carries out structural characterization to white crystal and white powder solid.Fig. 4 white solid powder
End1H NMR, Fig. 5 are the white crystal for being dried in vacuo chamber door and generating1H NMR.In Fig. 415.0ppm or 6.0ppm in H NMR
With at 10ppm characteristic peak positions and hydrogen peak area ratio can calculate the sodium hydrogensulfite addition of m-terephthal aldehyde in this example
The purity of product is only 50%, occur dissolved with insoluble matter to sample using deuterated DMSO.In Fig. 51The characteristic peak of H NMR
Show that time white crystals are m-terephthal aldehyde.Complex chart 4 and Fig. 5's1H NMR data shows in high-temperature heating drying process
Back reaction has occurred in the addition product of the sodium hydrogensulfite of the m-terephthal aldehyde of synthesis, generates NaHSO3 and m-terephthal aldehyde,
Be not suitable for being dried in vacuo synthetic product using 120 DEG C.
Claims (10)
1. a kind of method of synthesis aldehyde or methyl ketone and sodium hydrogensulfite addition product；It is characterized by:
By aldehyde or methyl ketone and NaHSO3Aqueous solution mixing is reacted, and reaction solution is added in solvent A, is then demultiplex out
Solvent B is added in upper solution, isolates solid, then sufficiently washed with solvent B, is finally dried to obtain white for upper solution
Powder solid is product；
The solvent A and solvent B are polar solvent, and the polarity of the solvent A is less than the polarity of solvent B；The solvent A must
It must be aprotic solvent.
2. according to the method for synthesis aldehyde or methyl ketone and sodium hydrogensulfite addition product described in claim 1；It is characterized by:
The solvent A is n,N-Dimethylformamide (DMF), n,N-dimethylacetamide (DMAc), N-Methyl pyrrolidone
(NMP), one or more of dimethyl sulfoxide (DMSO).
3. according to the method for synthesis aldehyde or methyl ketone and sodium hydrogensulfite addition product described in claim 1；It is characterized by:
The solvent B be ethyl alcohol, methanol, propyl alcohol, isopropanol, ether, tetrahydrofuran, acetonitrile, acetone, chloroform, methylene chloride, 1,
One or more of 1- dichloroethanes.
4. according to claim 1 the method；It is characterized by:
The temperature of solution is 20-30 DEG C after the reaction；The temperature of solvent A is 0~20 DEG C；The temperature of the upper solution is
20-30℃；The temperature of solvent B is 0~30 DEG C.
5. according to the method for claim 1, it is characterised in that:
The quality and NaHSO of aldehyde or methyl ketone in the reaction solution3Mass ratio be 1:1.5~1:3；
The NaHSO3Quality and water volume ratio be 0.5:1~0.1:1g/mL.
6. according to the method for claim 1, it is characterised in that:
The volume ratio of the quality and solvent A of the aldehyde or methyl ketone is 1:14~1:40g/mL；
The volume of the solvent A and the volume ratio of solvent B are 2:1~1:10.
7. according to the method for claim 1, it is characterised in that:
The separation method is one or more of centrifuge separation, natural filtration, vacuum filter or filters pressing；The drying
Method is forced air drying or vacuum drying；The drying temperature is room temperature~100 DEG C；The drying time is not less than 2 hours.
8. according to the method for claim 1, it is characterised in that:
It is described to use solvent B mode of washing as solvent B washing, repeated washing 6 times or more is added, or be added 30~45 after solvent B
The washing of DEG C heating stirring, be repeated 3 times it is above.
9. according to the method for claim 1, it is characterised in that: the aldehyde or methyl ketone and NaHSO3Reactant aqueous solution temperature
It is 0~80 DEG C；The reaction time is 5~60min.
10. according to the method for claim 1, it is characterised in that: the aldehyde or methyl ketone and sodium hydrogensulfite addition product
Structural formula it is as follows:
Wherein R1=H or CH3；R2The straight chained alkyl or C3-C18 branched alkyl or phenyl of=H or C1-C18 or
The wherein straight chained alkyl of R=H or C1-C6 or C3-C8 branched alkyl.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417937A (en) * | 2007-10-23 | 2009-04-29 | 中山大学 | Beta-aldehyde ketones antibacterial compounds and use thereof |
| CN105377950A (en) * | 2013-06-04 | 2016-03-02 | Pbi性能产品公司 | Method of making polybenzimidazole |
| CN105967987A (en) * | 2016-07-19 | 2016-09-28 | 扬州天辰精细化工有限公司 | Industrial aldehyde separating and purifying method |
-
2017
- 2017-12-18 CN CN201711365126.9A patent/CN109928899A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101417937A (en) * | 2007-10-23 | 2009-04-29 | 中山大学 | Beta-aldehyde ketones antibacterial compounds and use thereof |
| CN105377950A (en) * | 2013-06-04 | 2016-03-02 | Pbi性能产品公司 | Method of making polybenzimidazole |
| CN105967987A (en) * | 2016-07-19 | 2016-09-28 | 扬州天辰精细化工有限公司 | Industrial aldehyde separating and purifying method |
Non-Patent Citations (3)
| Title |
|---|
| 吴乾菁等: "羰基化合物与亚硫酸氢钠亲核加成反应实验的改进与探索", 《四川师范大学学报（自然科学版）》 * |
| 王金等: "羟基和甲氧基取代苯甲醛在亚硫酸氢钠-乙酸乙酯-水两相中分配系数的测定", 《中国药学杂志》 * |
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