CN110078771A - A kind of preparation method of iridium catalyst - Google Patents
A kind of preparation method of iridium catalyst Download PDFInfo
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- CN110078771A CN110078771A CN201910490325.5A CN201910490325A CN110078771A CN 110078771 A CN110078771 A CN 110078771A CN 201910490325 A CN201910490325 A CN 201910490325A CN 110078771 A CN110078771 A CN 110078771A
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- iridium
- preparation
- octadiene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
Abstract
The invention discloses a kind of iridium catalyst [IrCl (C8H12)]2Preparation method, include the following steps: under oxygen-free environment, the compound containing iridium and chlorine be dissolved in the water and is configured to iridium solution；Cyclo-octadiene is added in above-mentioned iridium solution, then reducing agent is slowly added dropwise, carries out reduction reaction, is added dropwise until being generated again without precipitating；Filtering solution, solid carry out evaporative crystallization after being washed with water, obtain [IrCl (C8H12)]2.The method of the present invention reaction time is short, product purity height and high income.
Description
Technical field
The present invention relates to technical field of organic chemistry, and in particular to noble metal homogeneous catalysis agent synthesizes field, in particular to
One kind [IrCl (C8H12)]2Preparation method.
Background technique
[IrCl(C8H12)]2It as a kind of noble metal homogeneous catalysis agent, while being also the presoma of a variety of iridium catalysts,
Chemical industry field is widely used.Especially in the industrial production of Herbicide Jing isopropyl methoxalamine, [IrCl (C8H12)]2It is
The catalyst precarsor of important asymmetric hydrogenation in synthesis process.
Herde, J, L (Inorganic syntheses, 1974,15,18) report 1,5 cyclo-octadiene iridium chlorides earliest
The synthesis of dimer, the process of reaction are that iridium chloride reacts 24 hours or more with ethyl alcohol under anaerobic counterflow condition.
In the preparation method of cyclo-octadiene iridium chloride disclosed in JP2006045089A, the mole dosage of 1,5 octadiene is chlorine
7-9 times for changing iridium, the purity of obtained 1,5 cyclo-octadiene iridium chloride dimers is lower, in order to remove impurity 1,3- ring pungent two
Alkene and Isosorbide-5-Nitrae cyclo-octadiene, are added a large amount of water at the end of reaction, and product is then precipitated, and this method cannot be made high-purity and must produce
Product.
US639980482 discloses a kind of preparation method of 1,5 cyclo-octadiene iridium chlorides, and reaction process is iridous chloride
Or iridic chloride and alcohol (carbon atom number 3-9) reflux are for a period of time, when the carbon atom number of alcohol is greater than in the preparation method
When, the alcohol in reaction is difficult to dissolve each other with water, a large amount of alcohol that is added (volume ratio of alcohol and water is that mono- 1:1 of 2:1 loses meaning,
And the problem of bringing post-processing: the cyclo-octadiene iridium chloride purity and active inequality that the preparation method obtains.
At present in reaction the reaction time it is long lead to that product purity is low, raw material usage amount is big, cannot recycle, high production cost,
Technique is not environmentally.
Therefore, it is necessary to develop one kind [IrCl (C8H12)]2Reaction time is short, [the IrCl of product purity height and high income
(C8H12)]2Preparation method.
Summary of the invention
Present invention aim to address existing [IrCl (C8H12)]2The generally existing reaction time, length caused in preparation method
Product purity is low, and raw material usage amount is big, cannot recycle, high production cost, technique not environmentally the problem of.
In order to solve the above technical problems, the technical scheme is that a kind of preparation method of iridium catalyst, including it is as follows
Step, the iridium catalyst are [IrCl (C8H12)]2；
S1, under oxygen-free environment, the compound containing iridium and chlorine is dissolved in the water and is configured to iridium solution；
S2, cyclo-octadiene is added in above-mentioned iridium solution, is stirred evenly；
S3, reducing agent is slowly added dropwise again, carries out reduction reaction, be added dropwise until being generated again without precipitating；
S4, S3 is obtained to solution filtering, solid carries out evaporative crystallization after being washed with water, obtains [IrCl (C8H12)]2。
In step S1, the compound containing iridium and chlorine is in iridium chloride, chloro-iridic acid, ammonium chloroiridate, iridium sodium chloride
It is at least one.The concentration of iridium solution is preferably 8%-30%.
In step S2, the molar ratio of the cyclo-octadiene of iridium and addition is 1:2.
In step S3, the reducing agent is selected from least one of hydrazine hydrate, borohydride hydride water solution.The temperature of reduction reaction
Degree is 50~100 DEG C, it is preferred that reduction temperature is 80-90 DEG C.And reducing agent is added dropwise with vigorous stirring.
In step S4, cyclo-octadiene is continued to use after filtrate liquid separation.
Water in above-mentioned steps is anaerobic water.
The method of the present invention reaction time is short, [IrCl (C8H12)]2Product purity is high and high income.The method of the present invention obtains
Complex of iridium purity be 99%, iridium content >=56.7%, elemental analysis carbon content be 28.32%~28.90%.
Detailed description of the invention
Fig. 1 is the nuclear-magnetism H-NMR figure of cyclo-octadiene iridium chloride prepared by comparative example 1.
Fig. 2 is the nuclear-magnetism H-NMR figure for obtaining cyclo-octadiene iridium chloride prepared by embodiment 1.
Fig. 3 is the nuclear-magnetism H-NMR figure for obtaining cyclo-octadiene iridium chloride prepared by embodiment 2.
Fig. 4 is the nuclear-magnetism H-NMR figure for obtaining cyclo-octadiene iridium chloride prepared by embodiment 3.
Fig. 5 is the nuclear-magnetism H-NMR figure for obtaining cyclo-octadiene iridium chloride prepared by embodiment 4.
Specific embodiment
In order to make it easy to understand, the present invention will be described in detail by specific embodiment below.It needs to refer in particular to
Out, these descriptions are only exemplary description, and are not meant to limit the scope of the invention.Opinion according to this specification
It states, many variations of the invention, change will be apparent from for those skilled in the art.
Embodiment 1
Iridium chloride is dissolved in anaerobic water, 10% iridium content solution is obtained, 2 times of molar ratio of cyclo-octadiene is added,
It oxygen free condition and is vigorously stirred lower dropwise addition hydrazine hydrate, 90 DEG C of reaction temperature, is added dropwise to and is generated without precipitating, filtering is washed with anaerobic
Filter cake is washed, evaporative crystallization obtains cyclo-octadiene iridium chloride [IrCl (C8H12)]2.Cyclo-octadiene continues to use after filtrate liquid separation.It receives
Rate 99.5%, quality purity 99%, iridium content: 56.71%, elemental analysis carbon content: 28.35%, nuclear-magnetism H-NMR is shown in attached drawing 2.
Embodiment 2
Chloro-iridic acid is dissolved in anaerobic water, 10% iridium content solution is obtained, 2 times of molar ratio of cyclo-octadiene is added,
It oxygen free condition and is vigorously stirred lower dropwise addition sodium borohydride, 80 DEG C of reaction temperature, is added dropwise to and is generated without precipitating, anaerobic water is used in filtering
Filter cake is washed, evaporative crystallization obtains cyclo-octadiene iridium chloride [IrCl (C8H12)]2.Cyclo-octadiene continues to use after filtrate liquid separation.
Yield 99.5%, quality purity 99%, iridium content: 56.77%, elemental analysis carbon content: 28.38%, nuclear-magnetism H-NMR is shown in attached drawing
3。
Embodiment 3
Iridium sodium chloride is dissolved in anaerobic water, 10% iridium content solution is obtained, 2 times of molar ratio of cyclo-octadiene is added,
In oxygen free condition and it is vigorously stirred lower dropwise addition hydrazine hydrate, 90 DEG C of reaction temperature, is added dropwise to and is generated without precipitating, anaerobic water is used in filtering
Filter cake is washed, evaporative crystallization obtains cyclo-octadiene iridium chloride [IrCl (C8H12)]2.Cyclo-octadiene continues to use after filtrate liquid separation.
Yield 99.5%, quality purity 99%, iridium content: 56.66%, elemental analysis carbon content: 28.32%, nuclear-magnetism H-NMR is shown in attached drawing
4。
Embodiment 4
Iridium chloride is dissolved in anaerobic water, 10% iridium content solution is obtained, 2 times of molar ratio of cyclo-octadiene is added,
It oxygen free condition and is vigorously stirred lower dropwise addition sodium borohydride solution, 80 DEG C of reaction temperature, is added dropwise to and is generated without precipitating, filtering, with nothing
Oxygen water washing filter cake, evaporative crystallization obtain cyclo-octadiene iridium chloride [IrCl (C8H12)]2.Cyclo-octadiene continues to make after filtrate liquid separation
With.Yield 99.5%, quality purity 99%, iridium content: 56.83%, elemental analysis carbon content: 28.41%, nuclear-magnetism H-NMR is shown in
Attached drawing 5.
Comparative example 1
[IrCl(C8H12)]2Ethanol procedure
Iridium chloride is dissolved in the mixed solution of anaerobic water and industrial alcohol, 2 times of molar ratio of cyclo-octadiene is added,
It is stirred at reflux under oxygen free condition 24 hours or more.It is cooled to room temperature, filters the solid of precipitation, and washed with cold methanol, it is dry.It receives
Rate 70%, quality purity 98%, iridium content: 56.08%, elemental analysis carbon content: 28.04%, nuclear-magnetism H-NMR is shown in attached drawing 1.
The foregoing examples are merely illustrative of the technical concept and features of the invention, its object is to allow the person skilled in the art to be
It cans understand the content of the present invention and implement it accordingly, it is not intended to limit the scope of the present invention.It is all smart according to the present invention
The equivalent transformation or modification that refreshing essence is done, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of preparation method of iridium catalyst, includes the following steps:
S1, under oxygen-free environment, the compound containing iridium and chlorine is dissolved in the water and is configured to iridium solution；
S2, cyclo-octadiene is added in above-mentioned iridium solution, is stirred evenly；
S3, reducing agent is slowly added dropwise again, carries out reduction reaction, be added dropwise until being generated again without precipitating；
S4, S3 is obtained to solution filtering, solid carries out evaporative crystallization after being washed with water, obtains [IrCl (C8H12)]2。
2. preparation method according to claim 1, which is characterized in that described to be selected containing the compound of iridium and chlorine in step S1
From at least one of iridium chloride, chloro-iridic acid, ammonium chloroiridate, iridium sodium chloride.
3. preparation method according to claim 1, which is characterized in that in step S1, the concentration of iridium solution is preferably 8%-
30%.
4. preparation method according to claim 1, which is characterized in that in step S2, the cyclo-octadiene of iridium and addition rubs
You are than being 1:2.
5. preparation method according to claim 1, which is characterized in that in step S3, the reducing agent is selected from hydrazine hydrate, boron
At least one of hydride aqueous solution.
6. preparation method according to claim 1, which is characterized in that in step S3, the temperature of reduction reaction is 50~100
DEG C,.
7. preparation method according to claim 1, which is characterized in that in step S3, reducing agent is added dropwise with vigorous stirring.
8. preparation method according to claim 1, which is characterized in that in step S4, cyclo-octadiene continues after filtrate liquid separation
It uses.
9. preparation method according to claim 1, which is characterized in that the water in above-mentioned steps is anaerobic water.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230999A (en) * | 2014-08-20 | 2014-12-24 | 昆明贵金属研究所 | Method for preparing dicarbonyl iridium acetylacetonate (I) |
| CN104926884A (en) * | 2015-04-23 | 2015-09-23 | 金川集团股份有限公司 | Preparation method of dichloro(1,5-cyclooctadiene) platinum (II) |
| CN105585596A (en) * | 2015-12-04 | 2016-05-18 | 江西省汉氏贵金属有限公司 | Preparation method of rhodium compounds |
| CN106220688A (en) * | 2016-08-15 | 2016-12-14 | 北京颖泰嘉和生物科技股份有限公司 | A kind of 1,5 dimeric preparation methoies of cyclo-octadiene iridium chloride |
| CN106380490A (en) * | 2016-09-09 | 2017-02-08 | 昆明理工大学 | One-step synthesis method of (1,5-cyclooctadiene)-dichloro iridium dipolymer |
| CN106496279A (en) * | 2016-09-09 | 2017-03-15 | 昆明理工大学 | The synthetic method of (1,5 cyclo-octadiene) two chloro palladium |
| CN106632496A (en) * | 2016-11-29 | 2017-05-10 | 金川集团股份有限公司 | Preparation method of (1,5-cyclooctadiene) rhodium chloride (I) dimers |
-
2019
- 2019-06-06 CN CN201910490325.5A patent/CN110078771B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104230999A (en) * | 2014-08-20 | 2014-12-24 | 昆明贵金属研究所 | Method for preparing dicarbonyl iridium acetylacetonate (I) |
| CN104926884A (en) * | 2015-04-23 | 2015-09-23 | 金川集团股份有限公司 | Preparation method of dichloro(1,5-cyclooctadiene) platinum (II) |
| CN105585596A (en) * | 2015-12-04 | 2016-05-18 | 江西省汉氏贵金属有限公司 | Preparation method of rhodium compounds |
| CN106220688A (en) * | 2016-08-15 | 2016-12-14 | 北京颖泰嘉和生物科技股份有限公司 | A kind of 1,5 dimeric preparation methoies of cyclo-octadiene iridium chloride |
| CN106380490A (en) * | 2016-09-09 | 2017-02-08 | 昆明理工大学 | One-step synthesis method of (1,5-cyclooctadiene)-dichloro iridium dipolymer |
| CN106496279A (en) * | 2016-09-09 | 2017-03-15 | 昆明理工大学 | The synthetic method of (1,5 cyclo-octadiene) two chloro palladium |
| CN106632496A (en) * | 2016-11-29 | 2017-05-10 | 金川集团股份有限公司 | Preparation method of (1,5-cyclooctadiene) rhodium chloride (I) dimers |
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