CN104478758A - Synthesis method of diisopropyl azodicarboxylate - Google Patents
Synthesis method of diisopropyl azodicarboxylate Download PDFInfo
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- CN104478758A CN104478758A CN201410683219.6A CN201410683219A CN104478758A CN 104478758 A CN104478758 A CN 104478758A CN 201410683219 A CN201410683219 A CN 201410683219A CN 104478758 A CN104478758 A CN 104478758A
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- diisopropyl azodiformate
- synthetic method
- diisopropyl
- massfraction
- azodiformate
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Abstract
The invention discloses a synthesis method of diisopropyl azodicarboxylate. The synthesis method comprises the following steps: (1) adding alkali and a solvent under protection of inert gases, sequentially adding carbazic acid isopropyl ester and diethyl carbonate, carrying out heating reaction at 100-180 DEGC for 2-6 hours, adjusting the pH value of a solution to 4.5-7.5 with acid, and carrying out suction filtration, so as to obtain hydrogenated diisopropyl azodiformate; and (2) adding 40%-50% of sulfuric acid solution to the hydrogenated diisopropyl azodiformate at -20 DEG C to 25 DEG C, dissolving, adding a catalyst, controlling the reaction temperature to -15 DEG C to -5 DEG C, dropwise adding 10%-15% of hydrogen peroxide until no heat is emitted, further reacting for 5-10 hours after dropwise adding is ended, quenching, extracting, washing to be neutral, drying, filtering, and concentrating to obtain the diisopropyl azodiformate. The synthesis method disclosed by the invention is clean and environmental friendly in raw material, mild in reaction condition, and few in byproducts; and the product is high in yield and beneficial to industrialized production.
Description
Technical field
The present invention relates to the synthetic method of diisopropyl azodiformate, belong to technical field of organic synthesis.
Background technology
Azoformic acid diester, be one roughly the same time with the widely used intermediate of azo and carboxyl functional group, in particular as Mitsunobu cyclization reagent, carry out Mitsunobu reaction for the synthesis of some important heterogeneous ring compounds.Diisopropyl azodiformate (being called for short DIAD), the important member of such cyclization reagent, diisopropyl azodiformate not only can be used for the synthesis of the products such as photosensitizers, polymerizing catalyst, sterilant, also can be used as liquid blowing agent, itself and plastic cement compatibility are good, degradation production is colourless, pollution-free, odorless, has a extensive future.
At present the synthetic method of disclosed diisopropyl azodiformate mainly with diamine dioctyl phthalate diisopropyl ester for raw material, adopt different conditions to carry out being oxidized and obtain, greatly, yield is low, the problem that environmental pollution is serious in these method ubiquity energy consumptions.Significantly improve today day by day serious with environmental problem at Public environmental attitude, old and with serious pollution method is very necessary to adopt new synthesis technique and method to replace in the past.
Summary of the invention
The object of the invention is for overcoming the deficiencies in the prior art, a kind of new diisopropyl azodiformate synthetic method is provided.
For achieving the above object, the present invention adopts following technical proposals:
A synthetic method for diisopropyl azodiformate, comprises the following steps:
(1) under protection of inert gas, add alkali and solvent, add carbazic acid isopropyl ester and diethyl carbonate successively, reacting by heating 2 ~ 6h at 100 ~ 180 DEG C, by solution acid for adjusting pH value to 4.5 ~ 7.5, suction filtration, obtains hydrodiazo dioctyl phthalate diisopropyl ester;
(2) at-20 DEG C ~ 25 DEG C, hydrodiazo dicarboxylate being added massfraction is in the sulphuric acid soln of 40% ~ 50%, after dissolving, adds catalyzer, control temperature of reaction at-15 DEG C ~-5 DEG C, drip the hydrogen peroxide extremely no longer heat release that massfraction is 10% ~ 15%, drip Bi Jixu and react 5 ~ 10h, cancellation, extraction, be washed to neutrality, drying, filters, and concentrates and obtains diisopropyl azodiformate.
Preferably, in step (1), described alkali is one or both in sodium methylate, sodium ethylate, potassium methylate, potassium ethylate.
Preferably, in step (1), the mol ratio of described alkali and carbazic acid isopropyl ester is (0.35 ~ 0.8): 1.
Preferably, in step (1), described solvent is dimethyl sulfoxide (DMSO) or tetramethylene sulfone.
Preferably, in step (1), the mol ratio of described diethyl carbonate and carbazic acid isopropyl ester is (1 ~ 1.2): 1.
Preferably, in step (1), described acid to be massfraction be 10% ~ 30% hydrochloric acid.
Preferably, in step (2), described catalyzer is one or both in bromine, Hydrogen bromide, Sodium Bromide, Potassium Bromide.
Preferably, in step (2), use sodium bisulfite or Sulfothiorine cancellation.
Compared with prior art, at least there is following advantage in the present invention:
(1) in synthetic method of the present invention, raw material clean environment firendly, cheap;
(2) reaction conditions is gentle, and by product is few, and product yield is high;
(3) product purity is high, can drop into next step reaction without purifying, therefore can scale operation, is conducive to suitability for industrialized production.
Embodiment
Below will describe the present invention.But these embodiments do not limit the present invention, the conversion in the method that those of ordinary skill in the art makes according to these embodiments is all included in protection scope of the present invention.
Embodiment 1
Under nitrogen protection, 40g sodium methylate and 300ml anhydrous dimethyl sulphoxide is added in there-necked flask, slowly add 100g carbazic acid isopropyl ester and 100g diethyl carbonate successively, be warming up to 120 DEG C of reaction 3h, cooling, be the salt acid for adjusting pH value to 5 of 10% by solution massfraction, suction filtration, obtains hydrodiazo dioctyl phthalate diisopropyl ester;
At-20 DEG C ~ 25 DEG C, it is in the sulphuric acid soln of 40% that hydrodiazo dioctyl phthalate diisopropyl ester is added 300ml massfraction, after dissolving, slowly add 5g bromine, then control temperature of reaction at-15 DEG C ~-5 DEG C, drip the hydrogen peroxide extremely no longer heat release that massfraction is 10%, drip Bi Jixu and react 6h, use sodium bisulfite cancellation, with dichloromethane extraction, organic layer is washed to neutrality, anhydrous sodium sulfate drying organic layer, filter, concentrate and obtain diisopropyl azodiformate 79.1g, yield: 92.6%, purity: 98.9%.
HNMR(CDCl
3，300MHz)δ:4.0(1H,m,CH)；1.2(6H,d,CH
3)。
Embodiment 2
Under nitrogen protection, 70g sodium ethylate and 350ml dry sulpholane is added in there-necked flask, slowly add 100g carbazic acid isopropyl ester and 120g diethyl carbonate successively, be warming up to 170 DEG C of reaction 4h, cooling, be the salt acid for adjusting pH value to 6 of 30% by solution massfraction, suction filtration, obtains hydrodiazo dioctyl phthalate diisopropyl ester;
At-20 DEG C ~ 25 DEG C, it is in the sulphuric acid soln of 45% that hydrodiazo dioctyl phthalate diisopropyl ester is added 350ml massfraction, after dissolving, slowly add 5g Hydrogen bromide, then control temperature of reaction at-15 DEG C ~-5 DEG C, drip the hydrogen peroxide extremely no longer heat release that massfraction is 15%, drip Bi Jixu and react 7h, use Sulfothiorine cancellation, with dichloromethane extraction, organic layer is washed to neutrality, anhydrous magnesium sulfate drying organic layer, filter, concentrate and obtain diisopropyl azodiformate 81.7g, yield: 95.6%, purity: 99.0%.
HNMR(CDCl
3，300MHz)δ:4.0(1H,m,CH)；1.2(6H,d,CH
3)。
Embodiment 3
Under nitrogen protection, 45g potassium methylate and 350ml dry sulpholane is added in there-necked flask, slowly add 100g carbazic acid isopropyl ester and 110g diethyl carbonate successively, be warming up to 150 DEG C of reaction 6h, cooling, be the salt acid for adjusting pH value to 7 of 20% by solution massfraction, suction filtration, obtains hydrodiazo dioctyl phthalate diisopropyl ester;
At-20 DEG C ~ 25 DEG C, it is in the sulphuric acid soln of 50% that hydrodiazo dioctyl phthalate diisopropyl ester is added 300ml massfraction, after dissolving, slowly add 5g Sodium Bromide, then control temperature of reaction at-15 DEG C ~-5 DEG C, drip the hydrogen peroxide extremely no longer heat release that massfraction is 12%, drip Bi Jixu and react 5h, use Sulfothiorine cancellation, with dichloromethane extraction, organic layer is washed to neutrality, anhydrous sodium sulfate drying organic layer, filter, concentrate and obtain diisopropyl azodiformate 79.6g, yield: 93.1%, purity: 99.1%.
HNMR(CDCl
3，300MHz)δ:4.0(1H,m,CH)；1.2(6H,d,CH
3)。
Embodiment 4
Under nitrogen protection, 45g potassium ethylate and 350ml anhydrous dimethyl sulphoxide is added in there-necked flask, slowly add 100g carbazic acid isopropyl ester and 110g diethyl carbonate successively, be warming up to 140 DEG C of reaction 5h, cooling, be the salt acid for adjusting pH value to 5 of 10% by solution massfraction, suction filtration, obtains hydrodiazo dioctyl phthalate diisopropyl ester;
At-20 DEG C ~ 25 DEG C, it is in the sulphuric acid soln of 48% that hydrodiazo dioctyl phthalate diisopropyl ester is added 320ml massfraction, after dissolving, slowly add 5g Potassium Bromide, then control temperature of reaction at-15 DEG C ~-5 DEG C, drip the hydrogen peroxide extremely no longer heat release that massfraction is 10%, drip Bi Jixu and react 10h, use sodium bisulfite cancellation, with dichloromethane extraction, organic layer is washed to neutrality, anhydrous magnesium sulfate drying organic layer, filter, concentrate and obtain diisopropyl azodiformate 79.0g, yield: 92.4%, purity: 98.8%.
HNMR(CDCl
3，300MHz)δ:4.0(1H,m,CH)；1.2(6H,d,CH
3)。
Embodiment 5
Under nitrogen protection, 60g sodium ethylate and 350ml dry sulpholane is added in there-necked flask, slowly add 100g carbazic acid isopropyl ester and 120g diethyl carbonate successively, be warming up to 180 DEG C of reaction 3h, cooling, be the salt acid for adjusting pH value to 6 of 20% by solution massfraction, suction filtration, obtains hydrodiazo dioctyl phthalate diisopropyl ester;
At-20 DEG C ~ 25 DEG C, it is in the sulphuric acid soln of 42% that hydrodiazo dioctyl phthalate diisopropyl ester is added 310ml massfraction, after dissolving, slowly add 5g Sodium Bromide, then control temperature of reaction at-15 DEG C ~-5 DEG C, drip the hydrogen peroxide extremely no longer heat release that massfraction is 12%, drip Bi Jixu and react 9h, use sodium bisulfite cancellation, with dichloromethane extraction, organic layer is washed to neutrality, anhydrous magnesium sulfate drying organic layer, filter, concentrate and obtain diisopropyl azodiformate 79.0g, yield: 92.4%, purity: 98.8%.
HNMR(CDCl
3，300MHz)δ:4.0(1H,m,CH)；1.2(6H,d,CH
3)。
Be to be understood that, although this specification sheets is described according to embodiment, but not each embodiment only comprises an independently technical scheme, this narrating mode of specification sheets is only for clarity sake, those skilled in the art should by specification sheets integrally, technical scheme in each embodiment also through appropriately combined, can form other embodiments that it will be appreciated by those skilled in the art that.
A series of detailed description listed is above only illustrating for feasibility embodiment of the present invention; they are also not used to limit the scope of the invention, all do not depart from the skill of the present invention equivalent implementations done of spirit or change all should be included within protection scope of the present invention.
Claims (8)
1. a synthetic method for diisopropyl azodiformate, is characterized in that: comprise the following steps:
(1) under protection of inert gas, add alkali and solvent, add carbazic acid isopropyl ester and diethyl carbonate successively, reacting by heating 2 ~ 6h at 100 ~ 180 DEG C, by solution acid for adjusting pH value to 4.5 ~ 7.5, suction filtration, obtains hydrodiazo dioctyl phthalate diisopropyl ester;
(2) at-20 DEG C ~ 25 DEG C, hydrodiazo dicarboxylate being added massfraction is in the sulphuric acid soln of 40% ~ 50%, after dissolving, adds catalyzer, control temperature of reaction at-15 DEG C ~-5 DEG C, drip the hydrogen peroxide extremely no longer heat release that massfraction is 10% ~ 15%, drip Bi Jixu and react 5 ~ 10h, cancellation, extraction, be washed to neutrality, drying, filters, and concentrates and obtains diisopropyl azodiformate.
2. the synthetic method of diisopropyl azodiformate according to claim 1, is characterized in that: in step (1), and described alkali is one or both in sodium methylate, sodium ethylate, potassium methylate, potassium ethylate.
3. the synthetic method of diisopropyl azodiformate according to claim 2, is characterized in that: in step (1), and the mol ratio of described alkali and carbazic acid isopropyl ester is (0.35 ~ 0.8): 1.
4. the synthetic method of diisopropyl azodiformate according to claim 1, is characterized in that: in step (1), and described solvent is dimethyl sulfoxide (DMSO) or tetramethylene sulfone.
5. the synthetic method of diisopropyl azodiformate according to claim 1, is characterized in that: in step (1), and the mol ratio of described diethyl carbonate and carbazic acid isopropyl ester is (1 ~ 1.2): 1.
6. the synthetic method of diisopropyl azodiformate according to claim 1, is characterized in that: in step (1), described acid to be massfraction be 10% ~ 30% hydrochloric acid.
7. the synthetic method of diisopropyl azodiformate according to claim 1, is characterized in that: in step (2), and described catalyzer is one or both in bromine, Hydrogen bromide, Sodium Bromide, Potassium Bromide.
8. the synthetic method of diisopropyl azodiformate according to claim 1, is characterized in that: in step (2), uses sodium bisulfite or Sulfothiorine cancellation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1012264A (en) * | 1963-08-01 | 1965-12-08 | Wallace & Tiernan Inc | Preparation of azodiformate diesters and novel secondary aliphatic diesters |
| CN101544633A (en) * | 2008-03-28 | 2009-09-30 | 南开大学 | Synthesis technology for N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole-5-methanamide |
| CN101717348A (en) * | 2009-12-03 | 2010-06-02 | 常州南京大学高新技术研究院 | Synthesis method of diisopropyl azodiformate |
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2014
- 2014-11-24 CN CN201410683219.6A patent/CN104478758A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1012264A (en) * | 1963-08-01 | 1965-12-08 | Wallace & Tiernan Inc | Preparation of azodiformate diesters and novel secondary aliphatic diesters |
| CN101544633A (en) * | 2008-03-28 | 2009-09-30 | 南开大学 | Synthesis technology for N-(5-methyl-1,3-thiazole-2-yl)-4-methyl-1,2,3-thiadiazole-5-methanamide |
| CN101717348A (en) * | 2009-12-03 | 2010-06-02 | 常州南京大学高新技术研究院 | Synthesis method of diisopropyl azodiformate |
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Application publication date: 20150401 |