CN1246297C - Synthesis of water soluble oxamonoamide - Google Patents
Synthesis of water soluble oxamonoamide Download PDFInfo
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- CN1246297C CN1246297C CN 200410056889 CN200410056889A CN1246297C CN 1246297 C CN1246297 C CN 1246297C CN 200410056889 CN200410056889 CN 200410056889 CN 200410056889 A CN200410056889 A CN 200410056889A CN 1246297 C CN1246297 C CN 1246297C
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- sweet
- water
- dimethylamine
- sweet acid
- acid
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Abstract
The present invention discloses a synthetic method of water soluble oxa-monoamide, which belongs to the technical field of preparing an amide compound in organic chemistry, and relates to applications for nuclear fuel reprocessing, high-level liquid waste processing and nuclide decontamination. The synthetic method has the key points that under the condition of low temperature and with 1, 4-dioxaneunder as a solvent, diethylene acid anhydride reacts respectively with dimethylamine, diethylamine and dipropylamine in the existence of pyridine; the obtained product is concentrated and acidified by hydrochloric acid to be separated out by crystallization; the product is recrystallized and purified in water or a mixed solvent of ethanol and aether; then oxa-monoamide which has favorable water solubility is obtained. The synthetic method has the characteristics of simple process, high yield, easy purification of product, etc., and is suitable for production and application of an industrial scale.
Description
Technical field
The invention belongs to the preparing technical field of amides in the organic chemistry, particularly relate to the synthesis method of a kind of water-soluble half amide oxide of in nuclear fuel reprocessing, high level liquid waste processing and nucleic decontamination, using.
Background technology
For the big cyclic crown ether of extraction agent and the pod ether of ester dissolubility, its synthetic method has more research at present, and has been applied to the extraction to some metal ion and radionuclide.In recent years discover the half amide oxide compounds with crown ether, pod ether is the same that metal ion is had good coordination ability, different is that it has better water solubility, utilizes these character, it can be used as reverse-extraction agent.General for the rarer report of the synthetic method of half amide oxide compounds, existing synthetic method is directly acid anhydrides and dialkylamine under refluxad to be reacted, generally obtain the mixture of half amide oxide, pod ether and two sweet acid, the low and separation difficulty of productive rate has limited its industrial application.
Summary of the invention
The object of the invention is to propose the synthetic method of water-soluble half amide oxide, it is characterized in that: the synthetic method of described water-soluble half amide oxide divided for three steps:
(1) glycol ether prepares two sweet acid: glycol ether is that the nitric acid oxidation of 10mol/L generates two sweet acid through concentration, and wherein the volume ratio of glycol ether and concentrated nitric acid is 1: 7～10;
(2) two sweet acid generate two sweet acid anhydrides: with two sweet acid and diacetyl oxide is 1: 5～7 to react the back and use the toluene crystallization in molar ratio, obtains two white sweet acid anhydrides crystal; Wherein the consumption that adds the toluene of 500ml by two sweet sour 50g adds toluene;
(3) synthetic half amide oxide: 1: 1 in molar ratio, react with dimethylamine, diethylamine or dipropyl amine respectively with two sweet acid anhydrides, with two sweet acid anhydrides and 1,4-dioxane mol ratio be 1: 12～15 1,4-dioxane solvent ice-water bath, drips mol ratio and is 1: 1.1～1.5 diethylamine, dipropyl amine or dimethylamine and the mixed solution of pyridine by temperature control 3-7 ℃, reacted stopped reaction when the pH value of solution value is 8-9 2-5 hour; Wherein dimethylamine then is that the limit drips pyridine limit feeding exsiccant dimethylamine gas; Steam in a large number 1 with rotatory evaporator, 4-dioxane solvent when treating that remaining thickness mother liquor becomes reddish-brown, is poured in the water tumbler, and the mol ratio that under agitation drips pyridine and hydrochloric acid is 1: 1.2～2 hydrochloric acid, separates out a large amount of white crystals; Till when the pH value of solution is 1-2, obtains the white plates crystallization and be target product oxa-list substituted amide, product is recrystallization in water.
The invention has the beneficial effects as follows under cold condition, with 1, the 4-dioxane is a solvent, react in the presence of pyridine with dimethylamine, diethylamine and dipropyl amine respectively by two sweet acid anhydrides, the product that obtains can be in water or in the mixed solvent of ethanol and ether recrystallization purifying, the gained half amide oxide has good water-solubility.This method has that process is simple, productive rate is high, product is easy to characteristics such as purifying, is suitable for plant-scale production and application.
Embodiment
The present invention proposes a kind of synthetic method of water-soluble half amide oxide, this method is raw material with the glycol ether, through oxidation, contract and get two sweet acid anhydrides, obtains acid amides with the dialkylamine reaction again.Its reaction formula is as follows:
Synthetic method divided for three steps:
(1) glycol ether prepares two sweet acid: glycol ether generates two sweet acid, (volume ratio of glycol ether and concentrated nitric acid is 1: 7～10) through concentrated nitric acid (concentration is 10mol/L) oxidation;
(2) two sweet acid generate two sweet acid anhydrides: the toluene crystallization is used in two sweet acid and diacetyl oxide (mol ratio is 1: 5～7) reaction back, obtained two sweet acid anhydrides crystal of white; Wherein the consumption that adds the toluene of 500ml by two sweet sour 50g adds toluene;
(3) synthetic half amide oxide: two sweet acid anhydrides react with dimethylamine, diethylamine or dipropyl amine (mol ratio is 1: 1) respectively, with 1,4-dioxane solvent (two sweet acid anhydrides and 1,4-dioxane mol ratio is 1: 12～15), 3-7 ℃ of ice-water bath temperature control, drip the mixed solution (mol ratio 1: 1.1 ~ 1.5) (wherein dimethylamine then is that the limit drips pyridine limit feeding exsiccant dimethylamine gas) of diethylamine, dipropyl amine or dimethylamine and pyridine, reacted stopped reaction when the pH value of solution value is 8-9 2-5 hour.Steam in a large number 1 with rotatory evaporator, 4-dioxane solvent when treating that remaining thickness mother liquor becomes reddish-brown, is poured in the water tumbler, and under agitation dripping hydrochloric acid (mol ratio of pyridine and hydrochloric acid is 1: 1.2～2) is separated out a large amount of white crystals; Till when the pH value of solution is 1-2, obtains the white plates crystallization and be target product oxa-list substituted amide, product can be in water recrystallization.
The present invention will be described in detail below in conjunction with embodiment, but embodiment can not produce any restriction to the present invention.
1. the preparation of two sweet acid
In the there-necked flask of 1000ml, add 200ml deionized water and 450ml concentrated nitric acid (concentration is 10mol/L) respectively, thermometer, return line and dropping funnel are installed, and are connected the acid gas retrieving arrangement.In the 250ml dropping funnel, add the 100ml glycol ether.Under induction stirring, drip several glycol ethers or ethanol initiation reaction earlier, when electric mantle is heated to the 80-90 ℃ of left and right sides, there are a large amount of brown gases to produce, stop heating; Remove electric mantle and change ice-water bath; Drip glycol ether then, regulate the temperature of rate of addition control reaction system, make it to maintain 60-70 ℃.Remove ice-water bath after dropwising, continue to make its reaction 1 hour.Be warmed up to 90-100 ℃ behind the reacting balance once more, reacted again 2 hours.
Steam excessive nitric acid, when pale brown look flue gas produces, add proper amount of deionized water.Repeat this process, till the nitric acid with the overwhelming majority steams.Then surplus solution is poured into beaker and placed, back suction filtration, separation, the recrystallization of separating out to be crystallized with ether washing crystal and dry, promptly obtains product two sweet acid.Altogether product 110g, fusing point is 142-144 ℃, productive rate 82%.
2. two sweet acid anhydrides is synthetic
In the there-necked flask that charged magnetic stirs, add 50g exsiccant two sweet acid crystals.Make solvent with diacetyl oxide, dropping 2-8 drips phosphoric acid and does the initiator initiation reaction.Heating keeps acetic anhydride to reflux, and continues to finish after 3 hours reaction, remove as much as possible solvent under reduced pressure with rotatory evaporator after, the residue mother liquor is used toluene 500ml recrystallization while hot, through suction filtration, drying, obtains two sweet acid anhydrides crystal.Altogether product 41g, fusing point is 93-95 ℃, productive rate is 91%.
3. half amide oxide is synthetic
In the there-necked flask reactor of 1000ml, add 1 of 50g two sweet acid anhydrides and 450ml, 4-dioxane solvent, induction stirring 1 hour, the dissolving acid anhydrides is to the solution clear.Induction stirring is used the ice-water bath temperature control to guarantee that reactant fully contacts, and drips the mixed solution (then is that the limit drips pyridine limit feeding exsiccant dimethylamine gas for dimethylamine) of diethylamine (dipropyl amine or dimethylamine) and pyridine with dropping funnel.Dripping excessive diethylamine (dipropyl amine) and pyridine makes reaction solution keep alkaline environment.Remove ice-water bath after dropwising, react after 3 hours, the pH value of solution value is the 8-9 stopped reaction.Product is poured in the matrass, steam 1 with rotatory evaporator, 4-dioxane solvent, treat that remaining thickness mother liquor is poured in the beaker when becoming reddish-brown and cool off, add deionized water again, under agitation slowly drip 1: 1 hydrochloric acid then, separate out a large amount of white crystals, continue dripping hydrochloric acid, till no longer separating out crystal.This moment, the pH value of solution was 1-2.The crystal that suction filtration is separated out obtains the white plates crystallization.
Two sweet acid anhydrides react with dimethylamine, diethylamine or dipropyl amine respectively, and obtaining corresponding methyl monoamide respectively is 52g, and fusing point 71-72 ℃, productive rate 75%,
1HNMR (D
2O, 600Mz): δ 4.1-4.2 (2s, 4H, 2CH
2), 2.7-2.8 (2s, 6H, 2CH
3).The ethyl monoamide is 69g, fusing point 68-70 ℃, and productive rate 85%,
1HNMR (CDCl
3, 600Mz): δ 4.38-4.20 (2s, 4H, 2CH
2), 3.43-3.18 (2dd, 4H, 2CH
2CH
3), 1.20-1.17 (2T, 6H, 2CH
2CH
3).The propyl group monoamide is 81g, fusing point 52-54 ℃, and productive rate 87%,
1HNMR (CDCl
3, 600Mz): δ 4.41-4.21 (2s, 4H, 2CH
2), 3.35-3.06 (2t, 4H, 2CH
2CH
2CH
3), 1.62-1.55 (m, 4H, 2CH
2CH
2CH
3), 0.96-0.88 (m, 6H, 2CH
2CH
2CH
3).
Claims (1)
1. the synthetic method of a water-soluble half amide oxide, it is characterized in that: the synthetic method of described water-soluble half amide oxide divided for three steps:
(1) glycol ether prepares two sweet acid: glycol ether is that the nitric acid oxidation of 10mol/L generates two sweet acid through concentration, and wherein the volume ratio of glycol ether and concentrated nitric acid is 1: 7～10;
(2) two sweet acid generate two sweet acid anhydrides: with two sweet acid and diacetyl oxide is 1: 5～7 to react the back and use the toluene crystallization in molar ratio, obtains two white sweet acid anhydrides crystal; Wherein the consumption that adds the toluene of 500ml by two sweet sour 50g adds toluene;
(3) synthetic half amide oxide: 1: 1 in molar ratio, react with dimethylamine, diethylamine or dipropyl amine respectively with two sweet acid anhydrides, with two sweet acid anhydrides and 1,4-dioxane mol ratio be 1: 12～15 1,4-dioxane solvent ice-water bath, drips mol ratio and is 1: 1.1～1.5 diethylamine, dipropyl amine or dimethylamine and the mixed solution of pyridine by temperature control 3-7 ℃, reacted stopped reaction when the pH value of solution value is 8-9 2-5 hour; Wherein dimethylamine then is that the limit drips pyridine limit feeding exsiccant dimethylamine gas; Steam in a large number 1 with rotatory evaporator, 4-dioxane solvent when treating that remaining thickness mother liquor becomes reddish-brown, is poured in the water tumbler, and the mol ratio that under agitation drips pyridine and hydrochloric acid is 1: 1.2～2 hydrochloric acid, separates out a large amount of white crystals; Till when the pH value of solution is 1-2, obtains the white plates crystallization and be target product oxa-list substituted amide, product is recrystallization in water.
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|---|---|---|---|
| CN 200410056889 CN1246297C (en) | 2004-08-30 | 2004-08-30 | Synthesis of water soluble oxamonoamide |
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|---|---|---|---|
| CN 200410056889 CN1246297C (en) | 2004-08-30 | 2004-08-30 | Synthesis of water soluble oxamonoamide |
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| CN1246297C true CN1246297C (en) | 2006-03-22 |
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| JP5679159B2 (en) * | 2010-07-05 | 2015-03-04 | 信越化学工業株式会社 | Method for synthesizing rare earth metal extractant and organic phase for solvent extraction of rare earth metal |
| JP5679158B2 (en) * | 2010-07-05 | 2015-03-04 | 信越化学工業株式会社 | Process for producing organic phase for solvent extraction of rare earth metals |
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