CN106543031A - A kind of synthetic method of diacetyldioxime - Google Patents
A kind of synthetic method of diacetyldioxime Download PDFInfo
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- CN106543031A CN106543031A CN201610950702.5A CN201610950702A CN106543031A CN 106543031 A CN106543031 A CN 106543031A CN 201610950702 A CN201610950702 A CN 201610950702A CN 106543031 A CN106543031 A CN 106543031A
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- diacetyl
- diacetyldioxime
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- hydrogen peroxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of new method of synthesis diacetyldioxime, step are as follows：1) 10～70 DEG C of isothermal reaction temperature is set, catalyst is added in etoh solvent and diacetyl mixed solution, 10～20 times for diacetyl quality of the ethanol consumption；2) strong aqua ammonia and hydrogen peroxide were added to into step 1 in 0.5～1 hour point for 1～3 time) mixed solution in, react 0.5～6 hour；The mol ratio of described diacetyl, hydrogen peroxide and ammonia is 1：2～3.5：2～4；The catalyst is HTS, and consumption is 1～4 times of diacetyl quality.Compared with prior art the invention has the beneficial effects as follows：(1) reactions steps are reduced, realizes the one-step synthesis of diacetyldioxime；(2) catalyst is pressed powder, easily separates from reaction system, and can be recycled, improves diacetyldioxime production efficiency to a certain extent；(3) the raw material low toxicity that used, harmless, byproduct of reaction is water, to environment almost non-hazardous, meets " green chemical industry " requirement.
Description
Technical field
The present invention relates to the compound for having nitrogen to be combined with oxygen, in particulars relate to a kind of synthetic method of diacetyldioxime.
Background technology
Diacetyldioxime (2,3-Butanedione dioxime) is a kind of important chemical reagent, in actual production and section
There is important purposes in learning research.Diacetyldioxime is used for analysis and the measure of nickel and palladium frequently as chelating agen；From cobalt and other
Nickel is separated in metal, from separate palladium in stannum, gold, rhenium, iridium；And the metal such as cyanide, nickel, palladium, cobalt, ferrum (II), rhenium (VII) from
The photometering of son.Further, since the nitrogen-atoms in diacetyldioxime complex are sp2 hydridization, its structure is biological with some
Upper important macrocyclic ligand (such as Vitamin B12 and Myoglobin) is similar, and its metal complex can be used for as model compound
The research of enzyme and catalyst.
Method that currently, diacetyldioxime is still reported according to W.L.Semon and V.R.Damerell (Org.Synth.1930,
10,22) producing, mainly comprising following step：(1), in the presence of sodium nitrite and sulphuric acid, ethanol is given birth to nitrite reaction
Into nitrous ether (ethyl nitrite)；(2) used as catalyst, butanone generates biacetyl monoxime with nitrous ether (ethyl nitrite) reaction to hydrochloric acid；(3) diacetyl list
Oxime reacts generation diacetyldioxime in a heated condition with azanol sodium monosulfate.
The method has following deficiency：(1) raw material corrosivity strong (sulphuric acid, hydrochloric acid), inflammable and explosive (nitrous ether (ethyl nitrite)), cause
Cancer (sodium nitrite)；(2) reaction involved by is homogeneous reaction, and step reaction is required for carrying out product separation, cumbersome；(3)
Three wastes discharge amount is big, and environmental pollution is serious.In today that problem of environmental pollution receives much concern, the method cannot meet " greenization
The requirement of work ".Therefore, New Research Method realizes that the green syt of diacetyldioxime is extremely urgent.However, at present with regard to this respect
There is not been reported for research work.
The content of the invention
It is an object of the invention to provide a kind of new method of synthesis diacetyldioxime, realizes the green syt of diacetyldioxime.
To reach above-mentioned purpose, the technical solution used in the present invention is as follows：
A kind of new method of synthesis diacetyldioxime, comprises the steps：
1) 10～70 DEG C of isothermal reaction temperature is set, catalyst is added in etoh solvent and diacetyl mixed solution,
10～20 times for diacetyl quality of the ethanol consumption；
2) strong aqua ammonia and hydrogen peroxide were added to into step 1 in 0.5～1 hour point for 1～3 time) mixed solution in, reaction
0.5～6 hour；The mol ratio of described diacetyl, hydrogen peroxide and ammonia is 1：2～3.5：2～4；The catalyst is titanium silicon
Molecular sieve, 1～4 times for diacetyl quality of consumption.
Step 1) preferably 30 DEG C of the isothermal reaction temperature.
Step 1) ethanol consumption is preferably 10 times of diacetyl quality.
Step 2) point 3 additions in the 1h of the strong aqua ammonia and hydrogen peroxide.
Step 2) described in response time be preferably 2h.
Step 2) described in the mol ratio of diacetyl, hydrogen peroxide and ammonia be preferably 1：2：3.
Step 2) described in HTS be TS-1, consumption is preferably 4 times of diacetyl quality.
Beneficial effects of the present invention compared with prior art：
(1) in preparation method provided by the present invention, ammonia and hydrogen peroxide are catalytically conveted to azanol by catalyst TS-1, raw
Into azanol directly with diacetyl reaction generate diacetyldioxime.Reactions steps are reduced, the one-step synthesis of diacetyldioxime are realized.
(2) catalyst TS-1 is pressed powder, easily separates from reaction system, and can be recycled, certain
Diacetyldioxime production efficiency is improve in degree.
(3) the raw material low toxicity that used, harmless, byproduct of reaction is water, to environment almost non-hazardous, meets current development
The requirement of " green chemical industry ".
Specific embodiment
In following examples：
The method that uses and instrument are being listed below, but should not be construed as restricted.
Diacetyl ammoxidation reaction products are quantitatively divided using Agilent Technologies 7890B gas chromatograpies
Analysis.
Conversion ratio, selective calculating：
The conversion ratio of diacetyl, acetic acid selectivity, diacetyldioxime selectivity and fourth two in reaction are calculated according to formula (1-4)
The selectivity of ketone monoxime.
(1) diacetyl conversion ratio：
Y1=(diacetyl total amount-diacetyl surpluses)/diacetyl total amount × 100%
(2) acetic acid selectivity：
Y2=acetic acid growing amount/diacetyl inversion quantity × 100%
(3) diacetyldioxime selectivity：
Y2=diacetyldioxime growing amount/diacetyl inversion quantity × 100%
(4) biacetyl monoxime selectivity：
Y2=biacetyl monoxime growing amount/diacetyl inversion quantity × 100%
Embodiment 1
40 DEG C of setting isothermal reaction temperature, 0.5gTS-1,0.5g diacetyl, 5.0g ethanol are added in there-necked flask, are used
1.1g concentrated ammonia solutions (25%) and 1.3g hydrogen peroxide (30%) are added in 1h by constant pressure funnel in three times.Start Deca
When timing, react 2h.
Embodiment 2
Titanium-silicon molecular sieve TS-1 chooses 0.8g, and other are with embodiment 1.
Embodiment 3
Titanium-silicon molecular sieve TS-1 chooses 1.0g, and other are with embodiment 1.
Embodiment 4
Titanium-silicon molecular sieve TS-1 chooses 1.4g, and other are with embodiment 1.
Embodiment 5
Titanium-silicon molecular sieve TS-1 chooses 1.8g, and other are with embodiment 1.
Embodiment 6
Titanium-silicon molecular sieve TS-1 chooses 2.0g, and other are with embodiment 1.
Embodiment 7
10 DEG C of setting isothermal reaction temperature, 2.0gTS-1,0.5g diacetyl, 5.0g ethanol are added in there-necked flask, are used
1.1g concentrated ammonia solutions (25%) and 1.3g hydrogen peroxide (30%) are added in 1h by constant pressure funnel in three times.Start Deca
When timing, react 2h.
Embodiment 8
20 DEG C of setting isothermal reaction temperature, other are with embodiment 7.
Embodiment 9
30 DEG C of setting isothermal reaction temperature, other are with embodiment 7.
Embodiment 10
Setting isothermal reaction temperature 50 C, other are with embodiment 7.
Embodiment 11
Setting isothermal reaction temperature 60 C, other are with embodiment 7.
Embodiment 12
Setting isothermal reaction temperature 70 C, other are with embodiment 7.
Embodiment 13
30 DEG C of setting isothermal reaction temperature, 2.0gTS-1,0.5g diacetyl, 5.0g ethanol are added in there-necked flask, are used
1.1g concentrated ammonia solutions (25%) and 1.3g hydrogen peroxide (30%) are added in 0.5h by constant pressure funnel in three times.Start drop
Added-time timing, reacts 0.5h.
Embodiment 14
Reaction 1.0h, other are with embodiment 13.
Embodiment 15
Reaction 4.0h, other are with embodiment 13.
Embodiment 16
Reaction 6.0h, other are with embodiment 13.
Embodiment 17
30 DEG C of setting isothermal reaction temperature, 2.0gTS-1,0.5g diacetyl, 5.0g ethanol are added in there-necked flask, are used
0.8g concentrated ammonia solutions (25%) and 1.3g hydrogen peroxide (30%) are added in 1h by constant pressure funnel in three times.Start Deca
When timing, react 2h.
Embodiment 18
The quality of concentrated ammonia solution (25%) is 1.0g, and other are with embodiment 17.
Embodiment 19
The quality of concentrated ammonia solution (25%) is 1.5g, and other are with embodiment 17.
Embodiment 20
The quality of concentrated ammonia solution (25%) is 1.7g, and other are with embodiment 17.
Embodiment 21
30 DEG C of setting isothermal reaction temperature, 2.0gTS-1,0.5g diacetyl, 5.0g ethanol are added in there-necked flask, are used
1.1g concentrated ammonia solutions (25%) and 1.6g hydrogen peroxide (30%) are added in 1h by constant pressure funnel in three times.Start Deca
When timing, react 2h.
Embodiment 22
The quality of hydrogen peroxide (30%) is 1.9g, and other are with embodiment 21.
Embodiment 23
The quality of hydrogen peroxide (30%) is 2.1g, and other are with embodiment 21.
Each embodiment evaluation result such as table 1：
Claims (7)
1. it is a kind of synthesis diacetyldioxime new method, it is characterised in that comprise the steps：
1) 10～70 DEG C of isothermal reaction temperature is set, catalyst is added in etoh solvent and diacetyl mixed solution, it is described
10～20 times for diacetyl quality of ethanol consumption；
2) strong aqua ammonia and hydrogen peroxide were added to into step 1 in 0.5～1 hour point for 1～3 time) mixed solution in, reaction 0.5
～6 hours；The mol ratio of described diacetyl, hydrogen peroxide and ammonia is 1：2～3.5：2～4；The catalyst is titanium silicon molecule
Sieve, 1～4 times for diacetyl quality of consumption.
2. a kind of new method of synthesis diacetyldioxime as claimed in claim 1, it is characterised in that step 1) isothermal reaction
Temperature is 30 DEG C.
3. a kind of new method of synthesis diacetyldioxime as claimed in claim 1, it is characterised in that step 1) ethanol consumption
For 10 times of diacetyl quality.
4. a kind of new method of synthesis diacetyldioxime as claimed in claim 1, it is characterised in that step 2) strong aqua ammonia and
Hydrogen peroxide divides 3 additions in 1h.
5. a kind of new method of synthesis diacetyldioxime as claimed in claim 1, it is characterised in that step 2) described in reaction when
Between be 2h.
6. a kind of new method of synthesis diacetyldioxime as claimed in claim 1, it is characterised in that step 2) described in fourth two
The mol ratio of ketone, hydrogen peroxide and ammonia is 1：2：3.
7. a kind of new method of synthesis diacetyldioxime as claimed in claim 1, it is characterised in that step 2) described in titanium silicon point
Son sieve is TS-1, and consumption is 4 times of diacetyl quality.
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| CN201610950702.5A CN106543031B (en) | 2016-10-27 | 2016-10-27 | A kind of synthetic method of dimethylglyoxime |
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| CN201610950702.5A CN106543031B (en) | 2016-10-27 | 2016-10-27 | A kind of synthetic method of dimethylglyoxime |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1069312A (en) * | 1964-02-26 | 1967-05-17 | Hercules Inc | Improvements in or relating to a process for preparing polyethers |
| JP2008203782A (en) * | 2007-02-22 | 2008-09-04 | Fujifilm Corp | Pattern-forming material |
| CN105921171A (en) * | 2016-04-29 | 2016-09-07 | 山西大学 | Method for improving stability of cyclohexanone ammoximation catalyst TS-1 molecular sieves |
-
2016
- 2016-10-27 CN CN201610950702.5A patent/CN106543031B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1069312A (en) * | 1964-02-26 | 1967-05-17 | Hercules Inc | Improvements in or relating to a process for preparing polyethers |
| JP2008203782A (en) * | 2007-02-22 | 2008-09-04 | Fujifilm Corp | Pattern-forming material |
| CN105921171A (en) * | 2016-04-29 | 2016-09-07 | 山西大学 | Method for improving stability of cyclohexanone ammoximation catalyst TS-1 molecular sieves |
Non-Patent Citations (4)
| Title |
|---|
| RAJENDRAN, GURUSAMY等: "The oxygen-18 isotope shift in nitrogen-15 NMR spectroscopy. 3. Effects of structure and solvent", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| ZAV"YALOV,S.I.，EZHOVA,G.I.: "Synthesis of aliphatic α-dioximes from oxazole derivatives", 《IZVESTIYA AKADEMII NAUK SSSR, SERIYA KHIMICHESKAYA》 * |
| 张妍: "改性TS-1型分子筛在氧化反应和胺化反应中的应用", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 张洁 等: "TS-1催化丁酮氨氧化制丁酮肟反应过程", 《化学工业与工程》 * |
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