CN110483584A - A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer - Google Patents
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer Download PDFInfo
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- CN110483584A CN110483584A CN201910958908.6A CN201910958908A CN110483584A CN 110483584 A CN110483584 A CN 110483584A CN 201910958908 A CN201910958908 A CN 201910958908A CN 110483584 A CN110483584 A CN 110483584A
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- iridium
- octadiene
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- methoxyl group
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- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000004912 1,5-cyclooctadiene Substances 0.000 title claims abstract description 49
- JAZCEXBNIYKZDI-UHFFFAOYSA-N [Ir+] Chemical class [Ir+] JAZCEXBNIYKZDI-UHFFFAOYSA-N 0.000 title claims abstract description 37
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000007864 aqueous solution Substances 0.000 claims abstract description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000000539 dimer Substances 0.000 claims abstract description 24
- RPOYPGDEQYFZNE-UHFFFAOYSA-J [Cl-].[Na+].[Ir+3].[Cl-].[Cl-].[Cl-] Chemical compound [Cl-].[Na+].[Ir+3].[Cl-].[Cl-].[Cl-] RPOYPGDEQYFZNE-UHFFFAOYSA-J 0.000 claims abstract description 21
- ORBBTCHHNMWMCP-UHFFFAOYSA-K cycloocta-1,5-diene trichloroiridium Chemical compound [Ir](Cl)(Cl)Cl.C1=CCCC=CCC1 ORBBTCHHNMWMCP-UHFFFAOYSA-K 0.000 claims abstract description 21
- 239000000243 solution Substances 0.000 claims abstract description 20
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 18
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000003729 cation exchange resin Substances 0.000 claims abstract description 15
- 238000005660 chlorination reaction Methods 0.000 claims abstract description 13
- 235000019441 ethanol Nutrition 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000010926 purge Methods 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims description 27
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 15
- 239000000460 chlorine Substances 0.000 claims description 15
- 229910052801 chlorine Inorganic materials 0.000 claims description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 21
- 229910052741 iridium Inorganic materials 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- 238000004587 chromatography analysis Methods 0.000 description 7
- 239000007791 liquid phase Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- -1 Aryl ketones Chemical class 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical class OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000010499 C–H functionalization reaction Methods 0.000 description 1
- 238000006161 Suzuki-Miyaura coupling reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000005841 biaryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006757 chemical reactions by type Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 108700008776 hepatitis C virus NS-5 Proteins 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps: (1) mixes iridium powder and sodium chloride, use N2After purging, obtained solid powder is dissolved in hydrochloric acid solution by chlorination, and stirring obtains iridium sodium chloride aqueous solution；(2) iridium sodium chloride aqueous solution is obtained into aqueous solution of chloraurate by acid cation exchange resin；(3) in N2Under protection, 1,5- cyclo-octadiene is added in ethyl alcohol, heats up, aqueous solution of chloraurate is added dropwise thereto, is stirred to react, is cooled to room temperature after being added dropwise, is crystallized, filtering obtains (1,5- cyclo-octadiene) iridium chloride (I) dimer；(4) potassium hydroxide is added in methanol, is stirred after heating, (1,5- cyclo-octadiene) iridium chloride (I) dimer is added thereto, react 3-6h, it is cooling, it filters, washing, vacuum drying.Method provided by the invention, product yield high, purity is high.
Description
Technical field
The invention belongs to chemosynthesis technical fields, and in particular to a kind of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) two
The preparation method of aggressiveness.
Background technique
Iridium is one of element most rare in the earth earth's crust, and average quality ratio only has 0.001/1000000th.Complex of iridium
It can be used to catalysis asymmetry hydrogenation reaction, this kind of catalyst has been used for synthesis of natural product, and can be difficult to hydrogen original
The substrate (such as non-functional dough alkene etc.) of change is hydrogenated to one of enantiomter.Iridium can form a variety of complexs,
It is played a role in Organic Light Emitting Diode (OLED).
(1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer is a kind of very important complex of iridium, and master is to be applied
Phenol is prepared in activation c h bond, such as from aromatic hydrocarbons.The reaction type of catalysis includes: to prepare heteroaryl-condensed indoles ring system, is made
For the inhibitor of HCV NS5B polymerase；Boronation reaction/Suzuki-Miyaura coupling reaction；Metalation-Suzuki is handed over
Coupling reaction is pitched, for synthesizing biaryl and miscellaneous double aryl；The reaction of four boronations；Height region and enantioselectivity asymmetry boron hydrogen
Change；Aryl ketones, benzaldehyde and benzylalcohol derivative occur by C-H activation adjacent silylated etc..
Preparing (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer in the prior art is usually by (1,5- cyclo-octadiene)
Iridium chloride (I) dimer and sodium methoxide, which are added in n-hexane to react, to be obtained.
Summary of the invention
The present invention provides a kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, is original with iridium powder
Material is sequentially prepared to obtain iridium sodium chloride, chloro-iridic acid, chloro-iridic acid and 1, and 5- ring zinc diene ligand complex generates (1,5- cyclo-octadiene)
Iridium chloride (I) dimer is stirred to react to obtain target product then in the methanol solution of potassium hydroxide.This method product is received
Rate is high, purity is high.
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) iridium powder and sodium chloride are mixed, uses N2After purging, it is passed through chlorine and carries out chlorination, the solid powder that will be obtained at room temperature
End is dissolved in hydrochloric acid solution, is stirred 1h, is obtained iridium sodium chloride aqueous solution；
(2) iridium sodium chloride aqueous solution is adsorbed, is replaced by acid cation exchange resin, then adjusted concentration and obtain
Aqueous solution of chloraurate；
(3) in N2Under protection, 1,5- cyclo-octadiene is added in ethyl alcohol, is warming up to 50-80 DEG C, then thereto described in dropwise addition
Aqueous solution of chloraurate, time for adding 0.5-1h are stirred to react 10-20h after being added dropwise, are cooled to room temperature, and crystallize, filtering,
Obtain (1,5- cyclo-octadiene) iridium chloride (I) dimer；
(4) potassium hydroxide is added in methanol, is warming up to 30-50 DEG C of stirring 1.5h, (1,5- ring pungent two is then added thereto
Alkene) iridium chloride (I) dimer, reacts 3-6h, is cooled to room temperature, filter, washing is dried in vacuo to get (1,5- ring pungent two is arrived
Alkene) (methoxyl group) iridium (I) dimer.
Preferably, the chlorine that is passed through carries out the concrete operations of chlorination to be first warming up to 400-700 DEG C, is passed through chlorine, instead
Answer 2-5h.
Preferably, the flow that is passed through of the chlorine is 100-300mL/min.
Preferably, the mass ratio of the iridium powder and sodium chloride is 10:(1.5-6.0).
Preferably, the concentration of the hydrochloric acid solution is 5-20 wt%%.
Preferably, step (2) aqueous solution of chloraurate is 0.3-0.6g/mL.
Preferably, the mass ratio of 1,5- cyclo-octadiene described in step (3) and ethyl alcohol is 1:(4-8), chloro-iridic acid and 1,5-
The molar ratio of cyclo-octadiene is 1:(1-3).
Preferably, step (4) potassium hydroxide, methanol mass ratio be 1:(5-10), (1,5- cyclo-octadiene) chlorination
The molar ratio of iridium (I) dimer and potassium hydroxide is 1:(5-15).
Preferably, step (4) the vacuum drying temperature is 25-30 DEG C, vacuum degree 0.06-0.08MPa, time are
2-3h。
Preferably, step (2) acid cation exchange resin is acid styrene type cation exchange resin, acidity
Any one in acrylic acid type cation exchange resin or acid phenolic type cation exchange resin.
Advantages of the present invention:
Method provided by the invention is simple to operation, environmentally protective, high income, (1,5- cyclo-octadiene) (methoxyl group) iridium of preparation
(I) dimer purity >=99%, yield are greater than 90%.
Specific embodiment
Embodiment 1
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) 10g iridium powder and 4.5g sodium chloride are mixed, is added in tube furnace, uses N2After purging 1-2min, it is first warming up to 500
DEG C, chlorine is passed through with the flow of 200mL/min, chlorination reaction 3h is carried out, then cools to room temperature, obtained solid powder is molten
Solution stirs 1h, obtains iridium sodium chloride aqueous solution in the hydrochloric acid solution of 60mL 10%；
(2) the iridium sodium chloride aqueous solution is passed through into acid styrene type cation exchange resin, is adsorbed, replaced, then
It adjusts concentration and obtains the aqueous solution of chloraurate of 0.4g/mL；
(3) in N2Under protection, by 11.2g 1,5- cyclo-octadiene is added in 80g ethyl alcohol, is warming up to 60 DEG C, is then dripped thereto
Add the aqueous solution of chloraurate, chloro-iridic acid and 1, the molar ratio of 5- cyclo-octadiene is 1:1, and time for adding control is added dropwise in 40min
After be stirred to react 20h, be cooled to room temperature, there is red crystals precipitation, filter, obtain (1,5- cyclo-octadiene) iridium chloride (I)
Dimer 17.1g is red crystals, yield 97.9%；
(4) 10g potassium hydroxide is added in 80g methanol, is warming up to 45 DEG C of stirring 1.5h, is then added at one time 15g thereto
(1,5- cyclo-octadiene) iridium chloride (I) dimer reacts 5h, is cooled to room temperature, and filters, and washing is true at 25 DEG C, 0.08MPa
The dry 2h of sky is yellow-green crystal, yield to get (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer 14.15g is arrived
95.6%；The chemical formula of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer is C18H30Ir2O2, structural formula is
；
Efficient liquid phase chromatographic analysis obtains, purity 99.2%；(1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer elemental analysis
Theoretical value: C: 32.63%, H: 4.53%, O: 4.83%, Ir:58.01%；It is C: 32.58% that actual element, which analyzes result,
H: 4.56%, O: 4.90%, Ir:57.96%.
Embodiment 2
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) 10g iridium powder and 1.53g sodium chloride are mixed, is added in tube furnace, uses N2After purging 1-2min, it is first warming up to 600
DEG C, chlorine is passed through with the flow of 300mL/min, chlorination reaction 2h is carried out, then cools to room temperature, obtained solid powder is molten
Solution stirs 1h, obtains iridium sodium chloride aqueous solution in the hydrochloric acid solution of 60mL 15%；
(2) the iridium sodium chloride aqueous solution is adsorbed, is replaced, then by Acidic acrylate's cation exchanger resin
It adjusts concentration and obtains the aqueous solution of chloraurate of 0.3g/mL；
(3) in N2Under protection, by 8.43g 1,5- cyclo-octadiene is added in 50g ethyl alcohol, is warming up to 60 DEG C, is then dripped thereto
Add the aqueous solution of chloraurate, chloro-iridic acid and 1, the molar ratio of 5- cyclo-octadiene is 1:3, and time for adding control is added dropwise in 30min
After be stirred to react 18h, be cooled to room temperature, there is red crystals precipitation, filter, obtain (1,5- cyclo-octadiene) iridium chloride (I)
Dimer 16.9g is red crystals, yield 96.8%；
(4) 8g potassium hydroxide is added in 65g methanol, is warming up to 35 DEG C of stirring 1.5h, is then added at one time 15g thereto
(1,5- cyclo-octadiene) iridium chloride (I) dimer reacts 6h, is cooled to room temperature, and filters, and washing is true at 30 DEG C, 0.06MPa
The dry 3h of sky is yellow-green crystal, yield to get (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer 13.90g is arrived
93.9%；
Efficient liquid phase chromatographic analysis obtains, purity 99.8%；It is C: 32.70%, H: 4.50%, O that actual element, which analyzes result:
4.93%, Ir:57.87%.
Embodiment 3
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) 10g iridium powder and 3.4g sodium chloride are mixed, is added in tube furnace, uses N2After purging 1-2min, it is first warming up to 700
DEG C, chlorine is passed through with the flow of 100mL/min, chlorination reaction 2h is carried out, then cools to room temperature, obtained solid powder is molten
Solution stirs 1h, obtains iridium sodium chloride aqueous solution in the hydrochloric acid solution of 60mL 10%；
(2) the iridium sodium chloride aqueous solution is passed through into acid phenolic type cation exchange resin, is adsorbed, replaced, is then adjusted
Section concentration obtains the aqueous solution of chloraurate of 0.5g/mL；
(3) in N2Under protection, by 14.05g 1,5- cyclo-octadiene is added in 80g ethyl alcohol, is warming up to 70 DEG C, then thereto
The aqueous solution of chloraurate, chloro-iridic acid and 1 is added dropwise, the molar ratio of 5- cyclo-octadiene is 1:3, and time for adding control is in 45min, drop
It is stirred to react 15h after adding, is cooled to room temperature, there is red crystals precipitation, filters, obtains (1,5- cyclo-octadiene) iridium chloride
(I) dimer 16.96g is red crystals, yield 97.1%；
(4) 15g potassium hydroxide is added in 100g methanol, is warming up to 50 DEG C of stirring 1.5h, is then added at one time 15g thereto
(1,5- cyclo-octadiene) iridium chloride (I) dimer reacts 4.5h, is cooled to room temperature, and filters, washing, at 25 DEG C, 0.07MPa
2h is dried in vacuo to get (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer 14.08g is arrived, is yellow-green crystal, yield
95.1%；
Efficient liquid phase chromatographic analysis obtains, purity 99.1%；It is C: 32.38%, H: 4.63%, O that actual element, which analyzes result:
5.21%, Ir:57.78%.
Embodiment 4
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) 10g iridium powder and 6g sodium chloride are mixed, is added in tube furnace, uses N2After purging 1-2min, 500 DEG C are first warming up to,
It is passed through chlorine with the flow of 250mL/min, chlorination reaction 2.5h is carried out, then cools to room temperature, obtained solid powder is molten
Solution stirs 1h, obtains iridium sodium chloride aqueous solution in the hydrochloric acid solution of 60mL 20%；
(2) the iridium sodium chloride aqueous solution is adsorbed, is replaced, then by Acidic acrylate's cation exchanger resin
It adjusts concentration and obtains the aqueous solution of chloraurate of 0.3g/mL；
(3) in N2Under protection, by 10.5g 1,5- cyclo-octadiene is added in 65g ethyl alcohol, is warming up to 60 DEG C, is then dripped thereto
Add the aqueous solution of chloraurate, chloro-iridic acid and 1, the molar ratio of 5- cyclo-octadiene is 1:2, and time for adding control is added dropwise in 50min
After be stirred to react 10h, be cooled to room temperature, there is red crystals precipitation, filter, obtain (1,5- cyclo-octadiene) iridium chloride (I)
Dimer 16.8g is red crystals, yield 96.4%；
(4) 12g potassium hydroxide is added in 80g methanol, is warming up to 40 DEG C of stirring 1.5h, is then added at one time 15g thereto
(1,5- cyclo-octadiene) iridium chloride (I) dimer reacts 4h, is cooled to room temperature, and filters, and washing is true at 30 DEG C, 0.08MPa
The dry 2h of sky is yellow-green crystal, yield to get (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer 14.12g is arrived
95.4%；
Efficient liquid phase chromatographic analysis obtains, purity 99.0%；It is C: 32.53%, H: 4.61%, O that actual element, which analyzes result:
4.83%, Ir:58.03%.
Embodiment 5
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) 10g iridium powder and 2.7g sodium chloride are mixed, is added in tube furnace, uses N2After purging 1-2min, it is first warming up to 650
DEG C, chlorine is passed through with the flow of 150mL/min, chlorination reaction 2h is carried out, then cools to room temperature, obtained solid powder is molten
Solution stirs 1h, obtains iridium sodium chloride aqueous solution in the hydrochloric acid solution of 60mL 8%；
(2) the iridium sodium chloride aqueous solution is passed through into acid phenolic type cation exchange resin, is adsorbed, replaced, is then adjusted
Section concentration obtains the aqueous solution of chloraurate of 0.5g/mL；
(3) in N2Under protection, by 9.23g 1,5- cyclo-octadiene is added in 60g ethyl alcohol, is warming up to 50 DEG C, is then dripped thereto
Add the aqueous solution of chloraurate, chloro-iridic acid and 1, the molar ratio of 5- cyclo-octadiene is 1:2, and time for adding control is added dropwise in 35min
After be stirred to react 14h, be cooled to room temperature, there is red crystals precipitation, filter, obtain (1,5- cyclo-octadiene) iridium chloride (I)
Dimer 16.56g is red crystals, yield 94.8%；
(4) 10g potassium hydroxide is added in 65g methanol, is warming up to 30 DEG C of stirring 1.5h, is then added at one time 15g thereto
(1,5- cyclo-octadiene) iridium chloride (I) dimer reacts 5h, is cooled to room temperature, and filters, and washing is true at 25 DEG C, 0.06MPa
The dry 3h of sky is yellow-green crystal, yield to get (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer 14.09g is arrived
95.2%；
Efficient liquid phase chromatographic analysis obtains, purity 99.6%；It is C: 32.55%, H: 4.59%, O that actual element, which analyzes result:
4.92%, Ir:57.94%.
Embodiment 6
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) 10g iridium powder and 3.6g sodium chloride are mixed, is added in tube furnace, uses N2After purging 1-2min, it is first warming up to 400
DEG C, chlorine is passed through with the flow of 100mL/min, chlorination reaction 5h is carried out, then cools to room temperature, obtained solid powder is molten
Solution stirs 1h, obtains iridium sodium chloride aqueous solution in the hydrochloric acid solution of 60mL 5%；
(2) the iridium sodium chloride aqueous solution is passed through into acid phenolic type cation exchange resin, is adsorbed, replaced, is then adjusted
Section concentration obtains the aqueous solution of chloraurate of 0.6g/mL；
(3) in N2Under protection, by 12.5g 1,5- cyclo-octadiene is added in 50g ethyl alcohol, is warming up to 80 DEG C, is then dripped thereto
Add the aqueous solution of chloraurate, chloro-iridic acid and 1, the molar ratio of 5- cyclo-octadiene is 1:2, and time for adding control is added dropwise in 60min
After be stirred to react 14h, be cooled to room temperature, there is red crystals precipitation, filter, obtain (1,5- cyclo-octadiene) iridium chloride (I)
Dimer 16.73g is red crystals, yield 95.8%；
(4) 6.3g potassium hydroxide is added in 63g methanol, is warming up to 30 DEG C of stirring 1.5h, is then added at one time 15g thereto
(1,5- cyclo-octadiene) iridium chloride (I) dimer reacts 3h, is cooled to room temperature, and filters, and washing is true at 25 DEG C, 0.06MPa
The dry 3h of sky is yellow-green crystal, yield to get (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer 14.00g is arrived
94.6%；
Efficient liquid phase chromatographic analysis obtains, purity 99.4%；It is C:32.71 %, H: 4.54%, O that actual element, which analyzes result:
4.79%, Ir:57.96%.
Embodiment 7
A kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, comprising the following steps:
(1) 10g iridium powder and 5.2g sodium chloride are mixed, is added in tube furnace, uses N2After purging 1-2min, it is first warming up to 400
DEG C, chlorine is passed through with the flow of 100mL/min, chlorination reaction 5h is carried out, then cools to room temperature, obtained solid powder is molten
Solution stirs 1h, obtains iridium sodium chloride aqueous solution in the hydrochloric acid solution of 60mL 5%；
(2) the iridium sodium chloride aqueous solution is passed through into acid styrene type cation exchange resin, is adsorbed, replaced, then
It adjusts concentration and obtains the aqueous solution of chloraurate of 0.6g/mL；
(3) in N2Under protection, by 12.5 g 1,5- cyclo-octadiene is added in 100g ethyl alcohol, is warming up to 80 DEG C, then thereto
The aqueous solution of chloraurate, chloro-iridic acid and 1 is added dropwise, the molar ratio of 5- cyclo-octadiene is 1:1, and time for adding control is in 60min, drop
It is stirred to react 14h after adding, is cooled to room temperature, there is red crystals precipitation, filters, obtains (1,5- cyclo-octadiene) iridium chloride
(I) dimer 16.63g is red crystals, yield 95.2%；
(4) 18.8g potassium hydroxide is added in 94 g methanol, is warming up to 30 DEG C of stirring 1.5h, is then added at one time thereto
15g (1,5- cyclo-octadiene) iridium chloride (I) dimer reacts 3h, is cooled to room temperature, and filters, washing, in 30 DEG C, 0.06MPa
Lower vacuum drying 3h is yellow-green crystal, yield to get (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer 14.03g is arrived
94.8%；
Efficient liquid phase chromatographic analysis obtains, purity 99.5%；It is C: 32.57%, H: 4.51%, O that actual element, which analyzes result:
4.85%, Ir:58.07%.
Claims (10)
1. a kind of preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, it is characterised in that: including following step
It is rapid:
(1) iridium powder and sodium chloride are mixed, uses N2After purging, it is passed through chlorine and carries out chlorination, the solid powder that will be obtained at room temperature
It is dissolved in hydrochloric acid solution, stirs 1h, obtain iridium sodium chloride aqueous solution；
(2) iridium sodium chloride aqueous solution is adsorbed, is replaced by acid cation exchange resin, then adjusted concentration and obtain
Aqueous solution of chloraurate；
(3) in N2Under protection, 1,5- cyclo-octadiene is added in ethyl alcohol, is warming up to 50-80 DEG C, then thereto described in dropwise addition
Aqueous solution of chloraurate, time for adding 0.5-1h are stirred to react 10-20h after being added dropwise, are cooled to room temperature, and crystallize, filtering,
Obtain (1,5- cyclo-octadiene) iridium chloride (I) dimer；
(4) potassium hydroxide is added in methanol, is warming up to 30-50 DEG C of stirring 1.5h, (1,5- ring pungent two is then added thereto
Alkene) iridium chloride (I) dimer, reacts 3-6h, is cooled to room temperature, filter, washing is dried in vacuo to get (1,5- ring pungent two is arrived
Alkene) (methoxyl group) iridium (I) dimer.
2. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In: the chlorine that is passed through carries out the concrete operations of chlorination to be first warming up to 400-700 DEG C, is passed through chlorine, reacts 2-5h.
3. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 2
In: the flow that is passed through of the chlorine is 100-300mL/min.
4. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In: the mass ratio of the iridium powder and sodium chloride is 10:(1.5-6.0).
5. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In: the concentration of the hydrochloric acid solution is 5-20wt%.
6. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In: step (2) aqueous solution of chloraurate is 0.3-0.6g/mL.
7. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In: the mass ratio of 1,5- cyclo-octadiene described in step (3) and ethyl alcohol is 1:(4-8), chloro-iridic acid and 1,5- cyclo-octadiene rubs
You are than being 1:(1-3).
8. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In the mass ratio of: step (4) potassium hydroxide, methanol be 1:(5-10), (1,5- cyclo-octadiene) iridium chloride (I) dimer with
The molar ratio of potassium hydroxide is 1:(5-15).
9. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In: step (4) the vacuum drying temperature be 25-30 DEG C, vacuum degree 0.06-0.08MPa, time 2-3h.
10. the preparation method of (1,5- cyclo-octadiene) (methoxyl group) iridium (I) dimer, feature exist according to claim 1
In: step (2) acid cation exchange resin be acid styrene type cation exchange resin, Acidic acrylate be sun from
Any one in sub-exchange resin or acid phenolic type cation exchange resin.
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| CN115141233A (en) * | 2022-06-23 | 2022-10-04 | 浙江微通催化新材料有限公司 | Synthesis method of bis (1, 5-cyclooctadiene) rhodium trifluoromethanesulfonate |
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