CN101817756A - Method for preparing para-N-hydroxymethyl aminobenzaldehyde - Google Patents
Method for preparing para-N-hydroxymethyl aminobenzaldehyde Download PDFInfo
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- CN101817756A CN101817756A CN201010154441A CN201010154441A CN101817756A CN 101817756 A CN101817756 A CN 101817756A CN 201010154441 A CN201010154441 A CN 201010154441A CN 201010154441 A CN201010154441 A CN 201010154441A CN 101817756 A CN101817756 A CN 101817756A
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Abstract
The invention discloses a method for preparing para-N-hydroxymethyl aminobenzaldehyde, which comprises the following steps of: putting Na2S and NaOH into water, heating the water to dissolve the Na2S and NaOH, adding sublimed sulfur into the solution and heating and boiling the solution to obtain Na2Sx solution; adding a catalytic amount of DMF into the ethanol solution of para-nitrotoluene, adding the Na2Sx solution dropwise into the ethanol solution under heating reflux and keeping the heating reflux; performing steam distillation and filtration and precipitating crystals after the solution is cooled to obtain para aminotenzaldehyde; and dissolving the para aminotenzaldehyde in the hot water, adding paraformal-dehyde into the solution, heating the solution for reaction, and filtering, drying and collecting the precipitated crystals to obtain the para-N-hydroxymethyl aminobenzaldehyde. The method has the advantages of reducing the auto-polycondensation of the para aminotenzaldehyde, precipitating the pure para aminotenzaldehyde directly for subsequent reaction, improving the yield coefficient of the para-N-hydroxymethyl aminobenzaldehyde and making simple the separation and purification of the para-N-hydroxymethyl aminobenzaldehyde; the para-N-hydroxymethyl aminobenzaldehyde prepared by the method has the characteristics of good crystalline form and easy collection and storage; and simultaneously the raw materials in the method are cheap, so production cost is reduced.
Description
Technical field
The invention belongs to vitochemical synthetic field, specifically be meant a kind of preparation method the N-hydroxymethyl aminobenzaldehyde.
Background technology
To most essential steps in the preparation process of N-hydroxymethyl aminobenzaldehyde is the purifying of p-Aminobenzaldehyde.The general spissated technology p-Aminobenzaldehyde of extraction that adopts carries out separation and purification in the prior art, so very easily causes intermolecular polycondensation.At present commercially available para aminotenzaldehyde is very serious from the polycondensation phenomenon simultaneously, and major part is water-fast yellowish-brown condensation polymer.The para aminotenzaldehyde not high with purity prepares the N-hydroxymethyl aminobenzaldehyde, not only can cause yield excessively low, and impurity also can be more, the separation and purification difficulty.
Summary of the invention
It is higher to the purpose of this invention is to provide a kind of yield, and the separate easily purifying to N-hydroxymethyl aminobenzaldehyde preparation method.
A kind of preparation method to the N-hydroxymethyl aminobenzaldehyde, its step comprises:
1) be that the solid NaOH that 1 part solid Na2S and molfraction are 3-5 part puts in the water that molfraction is 200-300 part with molfraction, heating is all dissolved solid, adding molfraction is 6-20 part sublimed sulfur again, is heated to obtain Na2Sx solution after the boiling reflux reaction is finished.
2) to containing the N that adds catalytic amount in the ethanolic solution that molfraction is 3-8 part para-nitrotoluene, dinethylformamide, under being heated to backflow, Na2Sx solution is added drop-wise in the ethanolic solution of above-mentioned para-nitrotoluene then, continues to keep heating reflux reaction; React and carry out steam distillation after complete to no longer dissolving of precipitation, filter insoluble matter, again the crystal of separating out after the settled solution cooling is para aminotenzaldehyde.
3) be that 1 part para aminotenzaldehyde dissolves in hot water with molfraction, adding molfraction in the solution again is the solid polyformaldehyde of 1-1.5 part, be heated to back flow reaction, the faint yellow acicular crystal that will separate out after reaction is finished filters, the dry collection namely obtains the hydroxymethyl aminobenzaldehyde to N-.
X in the described Na2Sx solution is 2-6.
Heating for dissolving temperature in the step 1) is 50-80 ℃.
Reflux temperature in the step 1) is 100 ℃, and the time is 20-40 minute.
Step 2) the reflux temperature in is 80 ℃, reacts 2-6 hour.
Reflux temperature in the step 3) is 100 ℃, reacts 30-60 minute.
The ethanolic soln concentration of the para-nitrotoluene step 2) is 2mol/L.
The gradation in 10-15 minute of solid polyformaldehyde in the step 3) adds.
Step 2) N in, the dinethylformamide add-on is 0.1-1mL.
Hydroxyl in the N-methylol compound has chemism, it can with protein in free amine group take place crosslinkedly, improve the fusing point of gelatin, use as the gelatin hardener.Transesterification reaction can also take place in the N-methylol compound, improves sensitive materials medical membrane machine tool intensity by a relatively large margin.Because the N-hydroxymethyl aminobenzaldehyde is contained a plurality of active groups of aldehyde radical, amido and hydroxyl, polytype organic chemical reactions can take place, so it or a kind of good medicine intermediate.
In the method for preparation to the N-hydroxymethyl aminobenzaldehyde, make Na among the present invention
2S
xWith the gentle reaction of para-nitrotoluene, reduced para aminotenzaldehyde from polycondensation, and can from solvent, separate out pure para aminotenzaldehyde and directly carry out next step reaction, output and the quality of para aminotenzaldehyde have been improved, and then improved yield to the N-hydroxymethyl aminobenzaldehyde, make the separation and purification to the N-hydroxymethyl aminobenzaldehyde also only need crystallization to obtain, thick product can reach commercially pure requirement.And with preparation method of the present invention obtain to N-hydroxymethyl aminobenzaldehyde good crystalline, easy Collection and conservation.The para-nitrotoluene raw material is also more cheap than para aminotenzaldehyde simultaneously, has therefore also reduced production cost.
Embodiment
By the following specific examples further illustrate the invention:
Embodiment 1
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 4g are that to be dissolved in 90mL water be among the 5.0mol to 0.1mol, being heated to 50 ℃ all dissolves solid, adding 4.8g is that the 0.15mol sublimed sulfur is heated to boiling reaction 20min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 2.33.Be that the 0.1mol para-nitrotoluene is dissolved in the 50mL industrial alcohol with 13.7g, the DMF (DMF) that adds 0.3mL is catalyst, be heated to 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 1.5h.Dropwise rear continuation back flow reaction 3.5h.Carry out wet distillation 3h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 9.9g is 0.082mol, yield is 81.8%.With the p-Aminobenzaldehyde 9.9g of preparation is that 0.082mol is dissolved in the 400mL hot water, add the Paraformaldehyde 96 powder 2.5g that grinds in 10min is 0.082mol in batches, then behind 100 ℃ of back flow reaction 30min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 11.3g is 0.075mol, and yield is 91.3%.
Embodiment 2
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 3g are that to be dissolved in 135mL water be among the 7.5mol to 0.075mol, being heated to 80 ℃ all dissolves solid, adding 6.4g is that the 0.2mol sublimed sulfur is heated to boiling reaction 40min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 3.6.Be that the 0.1mol para-nitrotoluene is dissolved in the 50mL industrial alcohol with 13.7g, the DMF (DMF) that adds 0.5mL is catalyst, heat 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 1.5h.Dropwise rear continuation back flow reaction 2h.Carry out wet distillation 6h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 10.3g is 0.085mol, yield is 85.1%.With the p-Aminobenzaldehyde 10.3g of preparation is that 0.085mol is dissolved in the 400mL hot water, add the Paraformaldehyde 96 powder 3.63g that grinds in 15min is 0.121mol in batches, then behind 100 ℃ of back flow reaction 60min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 12.1g is 0.08mol, and yield is 94.3%.
Embodiment 3
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 5g are that to be dissolved in 120mL water be among the 6.67mol to 0.125mol, being heated to 60 ℃ all dissolves solid, adding 12.0g is that the 0.375mol sublimed sulfur is heated to boiling reaction 30min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 4.57.Be that the 0.1mol para-nitrotoluene is dissolved in the 50mL industrial alcohol with 13.7g, the DMF (DMF) that adds 0.5mL is catalyst, be heated to 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 1.5h.Dropwise rear continuation back flow reaction 6h.Carry out wet distillation 3h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 10.6g is 0.088mol, yield is 87.6%.With the p-Aminobenzaldehyde 10.6g of preparation is that 0.088mol is dissolved in the 500mL hot water, add the Paraformaldehyde 96 powder 3.3g that grinds in 12min is 0.11mol in batches, then behind 100 ℃ of back flow reaction 40min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 12.7g is 0.084mol, and yield is 95.6%.
Embodiment 4
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 5g are that to be dissolved in 120mL water be among the 6.67mol to 0.125mol, being heated to 60 ℃ all dissolves solid, adding 6.4g is that the 0.2mol sublimed sulfur is heated to boiling reaction 30min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 2.57.Be that the 0.1mol para-nitrotoluene is dissolved in the 50mL industrial alcohol with 13.7g, the DMF (DMF) that adds 0.4mL is catalyst, be heated to 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 2.5h.Dropwise rear continuation back flow reaction 3h.Carry out wet distillation 3h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 10.3g is 0.085mol, yield is 85.1%.With the p-Aminobenzaldehyde 10.3g of preparation is that 0.085mol is dissolved in the 500mL hot water, add the Paraformaldehyde 96 powder 2.8g that grinds in 15min is 0.093mol in batches, then behind 100 ℃ of back flow reaction 60min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 11.8g is 0.078mol, and yield is 91.9%.
Embodiment 5
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 4g are that to be dissolved in 120mL water be among the 6.67mol to 0.10mol, being heated to 60 ℃ all dissolves solid, adding 8.0g is that the 0.25mol sublimed sulfur is heated to boiling reaction 30min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 3.67.Be that the 0.1mol para-nitrotoluene is dissolved in the 50mL industrial alcohol with 13.7g, the DMF (DMF) that adds 0.5mL is catalyst, heat 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 1h.Dropwise rear continuation back flow reaction 4h.Carry out wet distillation 3h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 10.6g is 0.088mol, yield is 87.6%.With the p-Aminobenzaldehyde 10.6g of preparation is that 0.088mol is dissolved in the 500mL hot water, add the Paraformaldehyde 96 powder 3.4g that grinds in 10min is 0.113mol in batches, then behind 100 ℃ of back flow reaction 50min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 12.4g is 0.082mol, and yield is 93.3%.
Embodiment 6
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 5g are that to be dissolved in 120mL water be among the 6.67mol to 0.125mol, being heated to 60 ℃ all dissolves solid, adding 16g is that the 0.5mol sublimed sulfur is heated to boiling reaction 30min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 6.Be that the 0.15mol para-nitrotoluene is dissolved in the 75mL industrial alcohol with 20.6g, the DMF (DMF) that adds 0.5mL is catalyst, be heated to 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 1h.Dropwise rear continuation back flow reaction 4h.Carry out wet distillation 3h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 15.25g is 0.126mol, yield is 84.0%.With the p-Aminobenzaldehyde 15.25g of preparation is that 0.126mol is dissolved in the 400mL hot water, add the Paraformaldehyde 96 powder 3.9g that grinds in 12min is 0.13mol in batches, then behind 100 ℃ of back flow reaction 50min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 18.1g is 0.12mol, and yield is 95.2%.
Embodiment 7
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 5g are that to be dissolved in 120mL water be among the 6.67mol to 0.125mol, being heated to 60 ℃ all dissolves solid, adding 4.8g is that the 0.15mol sublimed sulfur is heated to boiling reaction 30min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 2.Be that the 0.075mol para-nitrotoluene is dissolved in the 40mL industrial alcohol with 10.3g, the DMF (DMF) that adds 0.1mL is catalyst, be heated to 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 1h.Dropwise rear continuation back flow reaction 4h.Carry out wet distillation 3h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 7.38g is 0.061mol, yield is 81.3%.With the p-Aminobenzaldehyde 7.38g of preparation is that 0.061mol is dissolved in the 300mL hot water, add the Paraformaldehyde 96 powder 2.7g that grinds in 10min is 0.09mol in batches, then behind 100 ℃ of back flow reaction 30min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 8.3g is 0.055mol, and yield is 90.2%.
Embodiment 8
With Na
2S9H
2O (nine water cure sodium) 6g is that 0.025mol and NaOH (NaOH) 4g are that to be dissolved in 90mL water be among the 5.0mol to 0.1mol, being heated to 50 ℃ all dissolves solid, adding 4.8g is that the 0.15mol sublimed sulfur is heated to boiling reaction 20min again, is prepared into Na
2S
x(sodium polysulfide) solution, wherein can calculate X according to element conservation is 2.33.Be that the 0.2mol para-nitrotoluene is dissolved in the 100mL industrial alcohol with 27.4g, the DMF (DMF) that adds 1.0mL is catalyst, be heated to 80 ℃ of backflows after, again with the Na of above-mentioned preparation
2S
xSolution is added drop-wise in the ethanolic solution of para-nitrotoluene, dropwises in 1.5h.Dropwise rear continuation back flow reaction 3.5h.Carry out wet distillation 3h after reaction finishes, filtered while hot is fallen insolubles, after the settled solution cooling, separates out the crystal p-Aminobenzaldehyde, suction filtration, and obtaining p-Aminobenzaldehyde after drying in the shade is that 18.6g is 0.154mol, yield is 76.8%.With the p-Aminobenzaldehyde 18.6g of preparation is that 0.154mol is dissolved in the 500mL hot water, add the Paraformaldehyde 96 powder 6.9g that grinds in 15min is 0.23mol in batches, then behind 100 ℃ of back flow reaction 60min, separate out faint yellow needle-like crystal, suction filtration and oven dry, obtaining N-hydroxymethyl aminobenzaldehyde 20.4g is 0.135mol, and yield is 87.7%.
Claims (9)
1. preparation method to the N-hydroxymethyl aminobenzaldehyde, its step comprises:
1) with molfraction is 1 part solid Na
2S and molfraction are that the solid NaOH of 3-5 part puts in the water that molfraction is 200-300 part, and heating is all dissolved solid, and adding molfraction is 6-20 part sublimed sulfur again, are heated to obtain Na after the boiling reflux reaction is finished
2S
xSolution;
2) to containing the DMF that adds catalytic amount in the ethanolic solution that molfraction is 3-8 part para-nitrotoluene, be heated under the backflow Na then
2S
xSolution is added drop-wise in the ethanolic solution of above-mentioned para-nitrotoluene, continues to keep heating reflux reaction; React and carry out steam distillation after complete to no longer dissolving of precipitation, filter insoluble matter, again the crystal of separating out after the settled solution cooling is para aminotenzaldehyde;
3) be that 1 part para aminotenzaldehyde dissolves in hot water with molfraction, adding molfraction in the solution again is the solid polyformaldehyde of 1-1.5 part, be heated to back flow reaction, the faint yellow acicular crystal that will separate out after reaction is finished filters, the dry collection namely obtains the hydroxymethyl aminobenzaldehyde to N-.
2. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: described Na
2S
xX in the solution is 2-6.
3. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: the heating for dissolving temperature in the step 1) is 50-80 ℃.
4. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: the reflux temperature in the step 1) is 100 ℃, and the time is 20-40 minute.
5. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: step 2) in the reflux temperature be 80 ℃, reacted 2-6 hour.
6. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: the reflux temperature in the step 3) is 100 ℃, reacts 30-60 minute.
7. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: step 2) in the ethanolic soln concentration of para-nitrotoluene be 2mol/L.
8. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: the gradation in 10-15 minute of the solid polyformaldehyde in the step 3) adds.
9. the preparation method to the N-hydroxymethyl aminobenzaldehyde according to claim 1 is characterized in that: step 2) in N, the dinethylformamide add-on is 0.1-1mL.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
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CN108929239A (en) * | 2018-08-10 | 2018-12-04 | 辽宁红山化工股份有限公司 | A kind of preparation method of sodium polysulfide |
CN109082226A (en) * | 2018-06-29 | 2018-12-25 | 湖北大学 | A kind of preparation method of wetting discoloration super hydrophobic surface |
CN113979878A (en) * | 2021-10-29 | 2022-01-28 | 浙江工业大学 | Preparation method of 2-aminobenzaldehyde |
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2010
- 2010-04-20 CN CN201010154441A patent/CN101817756A/en active Pending
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN109082226A (en) * | 2018-06-29 | 2018-12-25 | 湖北大学 | A kind of preparation method of wetting discoloration super hydrophobic surface |
CN109082226B (en) * | 2018-06-29 | 2020-09-15 | 湖北大学 | Preparation method of wet color-changing super-hydrophobic surface |
CN108929239A (en) * | 2018-08-10 | 2018-12-04 | 辽宁红山化工股份有限公司 | A kind of preparation method of sodium polysulfide |
CN108929239B (en) * | 2018-08-10 | 2021-03-02 | 辽宁红山化工股份有限公司 | Preparation method of sodium polysulfide |
CN113979878A (en) * | 2021-10-29 | 2022-01-28 | 浙江工业大学 | Preparation method of 2-aminobenzaldehyde |
CN113979878B (en) * | 2021-10-29 | 2024-05-03 | 浙江工业大学 | Preparation method of 2-aminobenzaldehyde |
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Application publication date: 20100901 |