CN117801026A - Trimethyl platinum iodide and preparation method and application thereof - Google Patents
Trimethyl platinum iodide and preparation method and application thereof Download PDFInfo
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- BCSYXDNNYLPNJO-UHFFFAOYSA-M C[Pt](C)(C)I Chemical compound C[Pt](C)(C)I BCSYXDNNYLPNJO-UHFFFAOYSA-M 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 26
- -1 platinum halide Chemical class 0.000 claims abstract description 26
- 239000013078 crystal Substances 0.000 claims abstract description 22
- PAAZPARNPHGIKF-UHFFFAOYSA-N 1,2-dibromoethane Chemical compound BrCCBr PAAZPARNPHGIKF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 238000010791 quenching Methods 0.000 claims abstract description 15
- 230000000171 quenching effect Effects 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 13
- 230000011987 methylation Effects 0.000 claims abstract description 13
- 238000007069 methylation reaction Methods 0.000 claims abstract description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 229940071870 hydroiodic acid Drugs 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 9
- 229910052700 potassium Inorganic materials 0.000 claims description 9
- 239000011591 potassium Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000012043 crude product Substances 0.000 claims description 7
- 239000012022 methylating agents Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000001953 recrystallisation Methods 0.000 claims description 4
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- YGBYJRVGNBVTCQ-UHFFFAOYSA-N C[Pt](C)C.[CH]1C=CC=C1 Chemical compound C[Pt](C)C.[CH]1C=CC=C1 YGBYJRVGNBVTCQ-UHFFFAOYSA-N 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- DODHYCGLWKOXCD-UHFFFAOYSA-N C[Pt](C1(C=CC=C1)C)(C)C Chemical compound C[Pt](C1(C=CC=C1)C)(C)C DODHYCGLWKOXCD-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FBSNEJXXSJHKHX-UHFFFAOYSA-N CC1=C(C(C=C1)([Pt]C)C)C Chemical compound CC1=C(C(C=C1)([Pt]C)C)C FBSNEJXXSJHKHX-UHFFFAOYSA-N 0.000 description 1
- MEYPSDUZACCFQG-UHFFFAOYSA-N C[Pt+](C)C Chemical class C[Pt+](C)C MEYPSDUZACCFQG-UHFFFAOYSA-N 0.000 description 1
- FALJXSPLMPMHEL-UHFFFAOYSA-N C[Pt](C)C Chemical compound C[Pt](C)C FALJXSPLMPMHEL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- FGRFDPAACIWMNT-UHFFFAOYSA-N carbanide;cyclopenta-1,3-diene;platinum Chemical compound [CH3-].[CH3-].[CH3-].[Pt].C=1C=C[CH-]C=1 FGRFDPAACIWMNT-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- AXTNEYPUUFCBII-UHFFFAOYSA-N sodium;5-methylcyclopenta-1,3-diene Chemical compound [Na+].C[C-]1C=CC=C1 AXTNEYPUUFCBII-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Abstract
The invention belongs to the technical field of organic synthesis, and provides trimethyl platinum iodide, a preparation method and application thereof, wherein the preparation method comprises the following steps: under the protective atmosphere, mixing platinum halide with an organic solvent, and adding a methylation reagent into the mixed solution to react to obtain a reaction system; quenching reaction is carried out on the reaction system and 1, 2-dibromoethane, so as to obtain a quenched reaction product; quenching the reaction product and carrying out a post-treatment after the reaction with hydroiodic acid to obtain the trimethyl platinum iodide crystal. The method of the invention greatly reduces the using amount of the methylation reagent, simplifies the preparation process of the trimethylplatinum iodide, has the characteristics of high efficiency and easy purification of products, and solves the problems of complex synthesis steps and complex post-treatment of the trimethylplatinum iodide.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to trimethyl platinum iodide, and a preparation method and application thereof.
Background
The (trimethyl) methylcyclopentadienyl platinum (IV), the (trimethyl) cyclopentadienyl platinum (IV) and the (trimethyl) ethylcyclopentadienyl platinum (IV) and other series of cyclopentadienyl platinum organometallic complexes have the advantages of easy sublimation, easy decomposition and the like, and are widely applied to CVD technology for synthesizing low-dimensional platinum metal plating layers, supported catalysts, sensors and the like. In addition, cyclopentadienyl platinum organometallic complexes have also practical applications in the field of photocatalysis. Therefore, the optimization of the technical route of trimethylplatinum iodide as an important precursor for synthesizing cyclopentadienyl platinum organometallic complexes is of great value.
At present, the synthesis method of the trimethyl platinum iodide mainly comprises the following steps: the platinum tetrachloride reacts with methyl magnesium iodide at low temperature, then reacts with hydrochloric acid and potassium iodide, and the product is obtained after extraction, concentration, purification and crystallization. (1]Gilman.H,Lichtenwalter.M,Benkeser.R.A,Organoplatinum Compounds[J, journal ofthe American Chemical Society,1953,75 (9) [2]G.I.Zharkova,I.A.Baidina,et al.Volatile Fluorinated Trimethylplatinum (IV) beta-Diketonates: synthesis, properties, and Structure [ J ]. Polyheat, 2012,40 (1): 40-45 ]) wherein the formatting reagent methyl magnesium iodide has a large amount of byproducts after reaction, and requires the use of excessive amounts of hydrochloric acid and potassium iodide, which is complicated in steps, complicated in post-treatment, difficult in separating the product and low in yield.
Therefore, the development of the preparation method of the trimethylplatinum iodide, which has simple process and improves the yield, has great significance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide trimethyl platinum iodide, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of trimethyl platinum iodide, which comprises the following steps:
1) Under the protective atmosphere, mixing platinum halide with an organic solvent, and adding a methylation reagent into the mixed solution to react to obtain a reaction system;
2) Quenching reaction is carried out on the reaction system and 1, 2-dibromoethane, so as to obtain a quenched reaction product;
3) Quenching the reaction product and carrying out a post-treatment after the reaction with hydroiodic acid to obtain the trimethyl platinum iodide crystal.
Preferably, the platinum halide is one or more of potassium chloroplatinate, sodium chloroplatinate and platinum tetrachloride; the methylating agent is diethyl ether solution of methyl lithium, diethoxymethane solution of methyl lithium or toluene solution of trimethylaluminum.
Preferably, the organic solvent is one or more of diethyl ether, toluene, tetrahydrofuran, acetone and ethyl acetate.
Preferably, the molar ratio of platinum halide to methylating agent is 1: 7-20; the mass volume ratio of the platinum halide to the organic solvent is 1g: 15-25 mL.
Preferably, in the step 1), the mixing time is 30-60 min, the mixing temperature is-18-0 ℃, and the reaction time is 10-14 h;
when adding the methylation reagent, the temperature of the mixed solution is-18-0 ℃, and the time for adding the methylation reagent is 4-16 hours.
Preferably, in step 2), the molar ratio of the 1, 2-dibromoethane to the platinum halide in step 1) is 3 to 7:1, the quenching reaction time is 0.5-1 h.
Preferably, in the step 3), the mass ratio of the hydroiodic acid to the platinum halide in the step 1) is 0.4-0.8:1, and the reaction time is 1-2 hours.
Preferably, the specific process of the post-treatment in the step 3) is as follows: and sequentially performing spin drying, washing and filtering on the reaction liquid obtained by the reaction to obtain a crude product, and sequentially performing recrystallization, filtering and drying on the crude product to obtain the trimethyl platinum iodide crystal.
The invention also provides the trimethyl platinum iodide prepared by the preparation method.
The invention also provides application of the trimethyl platinum iodide in preparation of trimethyl (methylcyclopentadienyl) platinum.
The beneficial effects of the invention include:
the invention provides a preparation method of trimethyl platinum iodide, which is a synthesis precursor of a metal platinum complex used for a Chemical Vapor Deposition (CVD) process, wherein platinum halide reacts with a methylation reagent, 1, 2-dibromoethane is used for quenching the rest methylation reagent, then the reaction product further reacts with hydroiodic acid, and the trimethyl platinum iodide is obtained after purification and separation, wherein the yield can reach more than 90 percent according to the feeding amount of the metal platinum. The method of the invention greatly reduces the using amount of the methylation reagent, simplifies the preparation process of the trimethylplatinum iodide, has the characteristics of high efficiency and easy purification of products, solves the problems of complex synthesis steps and complex post-treatment of the trimethylplatinum iodide, and provides possibility for the industrialized production of the trimethylplatinum iodide.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of a trimethylplatinum iodide crystal obtained in example 1.
Detailed Description
The invention provides a preparation method of trimethyl platinum iodide, which comprises the following steps:
1) Under the protective atmosphere, mixing platinum halide with an organic solvent, and adding a methylation reagent into the mixed solution to react to obtain a reaction system;
2) Quenching reaction is carried out on the reaction system and 1, 2-dibromoethane, so as to obtain a quenched reaction product;
3) Quenching the reaction product and carrying out a post-treatment after the reaction with hydroiodic acid to obtain the trimethyl platinum iodide crystal.
In the invention, the platinum halide is preferably one or more of potassium chloroplatinate, sodium chloroplatinate and platinum tetrachloride; the methylating agent is preferably an ether solution of methyllithium, a diethoxymethane solution of methyllithium or a toluene solution of trimethylaluminum.
In the present invention, the organic solvent is preferably one or more of diethyl ether, toluene, tetrahydrofuran, acetone and ethyl acetate.
In the present invention, the molar ratio of platinum halide to methylating agent is preferably 1:7 to 20, more preferably 1:9 to 18, more preferably 1: 12-15; the mass volume ratio of the platinum halide to the organic solvent is preferably 1g:15 to 25mL, more preferably 1g:18 to 22mL, more preferably 1g:20mL.
In step 1) of the present invention, the mixing time is preferably 30 to 60 minutes, more preferably 40 to 50 minutes; the mixing temperature is preferably-18 to 0 ℃, more preferably-15 to-5 ℃, and even more preferably-12 to-8 ℃; the reaction time is preferably 10 to 14 hours, more preferably 11 to 13 hours, and still more preferably 12 hours; the reaction temperature is preferably 15 to 35 ℃, and more preferably 20 to 30 ℃;
when the methylation reagent is added, the temperature of the mixed solution is preferably-18-0 ℃, more preferably-15-5 ℃, and even more preferably-12-8 ℃; the time for adding the methylating agent is preferably 4 to 16 hours, more preferably 6 to 14 hours, and still more preferably 8 to 12 hours.
In step 1) of the present invention, the protective atmosphere is preferably nitrogen or argon.
In step 2) of the present invention, the molar ratio of the 1, 2-dibromoethane to the platinum halide in step 1) is preferably 3 to 7:1, more preferably 4 to 6:1, more preferably 5:1, a step of; the quenching reaction time is preferably 0.5 to 1 hour, more preferably 0.75 hour.
In the step 3) of the present invention, the mass ratio of the hydroiodic acid to the platinum halide in the step 1) is preferably 0.4 to 0.8:1, more preferably 0.5 to 0.7:1, more preferably 0.6:1, a step of; the reaction time is preferably 1 to 2 hours, more preferably 1.5 hours.
In the present invention, the specific process of the post-treatment in step 3) is preferably: sequentially performing spin drying, washing and filtering on the reaction liquid obtained by the reaction to obtain a crude product, and sequentially performing recrystallization, filtering and drying on the crude product to obtain a trimethyl platinum iodide crystal; the reagent used for washing is preferably acetone; the crude product is light yellow solid powder; the reagent for recrystallization is preferably diethyl ether or toluene; the trimethylplatinum iodide crystals are pale yellow crystals.
The invention also provides the trimethyl platinum iodide prepared by the preparation method.
The invention also provides application of the trimethyl platinum iodide in preparation of trimethyl (methylcyclopentadienyl) platinum.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
0.5g of sodium chloroplatinate and 10mL of toluene were put into a single-necked flask equipped with a magnet, nitrogen was purged 3 times, and the flask was left to stand at-10℃and stirred at a rate of 1200rpm for 40 minutes to obtain a mixed solution. 3.3mL of 2.5mol/L diethyl ether solution of methyllithium was slowly pressed into a bottle by a double-ended needle using nitrogen at-10℃for 6 hours, and reacted at 25℃for 12 hours after all the diethyl ether solution of methyllithium was added to obtain a reaction system.
1, 2-dibromoethane (the mol ratio of the 1, 2-dibromoethane to the platinum halide is 5:1) is slowly injected into the reaction system at the rate of 1mL/20s under the ice bath condition, and the quenching reaction is carried out for 0.5h. 0.14mL of hydroiodic acid with the concentration of 55wt% is added into the obtained quenched reaction product, and the reaction is continued for 2 hours at 25 ℃ to obtain a reaction solution.
The reaction solution was subjected to solvent removal using a rotary evaporator at a rate of 800rpm under a vacuum of-0.1 MPa at 40℃and washed with acetone, and filtered to obtain a pale yellow solid. The pale yellow solid is recrystallized by diethyl ether, filtered and dried overnight at 40 ℃ and the vacuum degree of minus 0.1MPa to obtain the trimethyl platinum iodide crystal.
The mass of the trimethylplatinum iodide crystal of this example was 0.234g, and the product yield was 62.3% based on sodium chloroplatinate.
The nuclear magnetic resonance spectrum of the trimethylplatinum iodide crystal obtained in example 1 is shown in FIG. 1.
Example 2
0.5g of potassium chloroplatinate and 10mL of tetrahydrofuran were charged into a single-necked flask equipped with a magnet, nitrogen was purged 3 times, and the flask was left to stand at-0℃and stirred at a rate of 1200rpm for 40 minutes to obtain a mixed solution. At-0 ℃, 7.5mL of 2.5mol/L diethoxymethane solution of methyl lithium is slowly pressed into a bottle through a double-ended needle by using nitrogen, the total addition time of the diethoxymethane solution of the methyl lithium is 10 hours, and the reaction is carried out at 20 ℃ for 14 hours after the total addition, so as to obtain a reaction system.
1, 2-dibromoethane (the molar ratio of the 1, 2-dibromoethane to the platinum halide is 4:1) is slowly injected into the reaction system at a rate of 1mL/20s under the ice bath condition, and the quenching reaction is carried out for 0.5h. 0.17ml55wt% of hydroiodic acid was added to the obtained quenched reaction product, and the reaction was continued at 20℃for 2 hours to obtain a reaction solution.
The reaction solution was subjected to solvent removal using a rotary evaporator at a rate of 800rpm under a vacuum of-0.1 MPa at 40℃and washed with acetone, and filtered to obtain a pale yellow solid. The pale yellow solid is recrystallized by toluene, filtered and dried overnight at 40 ℃ and the vacuum degree of minus 0.1MPa to obtain the trimethyl platinum iodide crystal.
The mass of the trimethylplatinum iodide crystal of this example was 0.264g, and the product yield based on potassium chloroplatinate was 70%.
Example 3
0.5g of potassium chloroplatinate and 10mL of tetrahydrofuran were charged into a single-necked flask equipped with a magnet, nitrogen was purged 3 times, and the flask was left to stand at-0℃and stirred at a rate of 1200rpm for 40 minutes to obtain a mixed solution. At-0 ℃, 7.5mL of 2.5mol/L toluene solution of trimethylaluminum is slowly pressed into a bottle through a double-ended needle by using nitrogen, the total time of adding the toluene solution of trimethylaluminum is 8 hours, and the reaction is carried out at 20 ℃ for 12 hours after the total time of adding the toluene solution of trimethylaluminum, so as to obtain a reaction system.
1, 2-dibromoethane (the molar ratio of the 1, 2-dibromoethane to the platinum halide is 6:1) is slowly injected into the reaction system at a rate of 1mL/20s under the ice bath condition, and the quenching reaction is carried out for 0.5h. 0.154ml55wt% of hydroiodic acid was added to the obtained quenched reaction product, and the reaction was continued at 20℃for 2 hours to obtain a reaction solution.
The reaction solution was subjected to solvent removal using a rotary evaporator at a rate of 800rpm under a vacuum of-0.1 MPa at 40℃and washed with acetone, and filtered to obtain a pale yellow solid. The pale yellow solid is recrystallized by toluene, filtered and dried overnight at 40 ℃ and the vacuum degree of minus 0.1MPa to obtain the trimethyl platinum iodide crystal.
The mass of the trimethylplatinum iodide crystal of this example was 0.338g, and the product yield based on potassium chloroplatinate was 89.7%.
Example 4
5g of potassium chloroplatinate and 100mL of tetrahydrofuran were put into a single-necked flask equipped with a magnet, nitrogen was purged 3 times, and the flask was placed at-0℃and stirred at a rate of 1200rpm for 40 minutes to obtain a mixed solution. 75mL of 2.5mol/L diethyl ether solution of methyllithium was slowly pressed into a bottle by a double-ended needle using nitrogen at-0℃for 7 hours, and reacted at 20℃for 12 hours after all the diethyl ether solution of methyllithium was added to obtain a reaction system.
1, 2-dibromoethane (the molar ratio of the 1, 2-dibromoethane to the platinum halide is 5:1) is slowly injected into the reaction system at a rate of 1mL/20s under the ice bath condition, and the reaction is quenched for 1h. 1.54ml of 55wt% hydriodic acid was added to the obtained quenched reaction product, and the reaction was continued at 20℃for 2 hours to obtain a reaction solution.
The reaction solution was subjected to solvent removal using a rotary evaporator at a rate of 800rpm under a vacuum of-0.1 MPa at 40℃and washed with acetone, and filtered to obtain a pale yellow solid. The pale yellow solid is recrystallized by toluene, filtered and dried overnight at 40 ℃ and the vacuum degree of minus 0.1MPa to obtain the trimethyl platinum iodide crystal.
The mass of the trimethylplatinum iodide crystal of this example was 3.3g, and the product yield based on potassium chloroplatinate was 87.5%.
Application example 1
1g of the trimethylplatinum iodide crystal of example 1 and 20mL of tetrahydrofuran were charged into a single-necked flask equipped with a magnet, nitrogen was purged 3 times, and stirred at 25℃for 40 minutes.
3mL of a 1mol/L solution of methylcyclopentadienyl sodium in tetrahydrofuran was added to the reaction system at a rate of 1mL/20s using a syringe, and the reaction was carried out at 25℃for 2 hours in the absence of light. After the reaction is completed, the product is taken out, dried by a rotary evaporator, sublimated for 2 hours at 75 ℃ and condensed and received at-50 ℃. The white solid collected on the sublimator was collected as trimethyl (methylcyclopentadienyl) platinum crystals.
The mass of the trimethylplatinum (methylcyclopentadienyl) crystals was 0.79g, and the product yield based on trimethylplatinum iodide was 91.2%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the trimethyl platinum iodide is characterized by comprising the following steps:
1) Under the protective atmosphere, mixing platinum halide with an organic solvent, and adding a methylation reagent into the mixed solution to react to obtain a reaction system;
2) Quenching reaction is carried out on the reaction system and 1, 2-dibromoethane, so as to obtain a quenched reaction product;
3) Quenching the reaction product and carrying out a post-treatment after the reaction with hydroiodic acid to obtain the trimethyl platinum iodide crystal.
2. The preparation method according to claim 1, wherein the platinum halide is one or more of potassium chloroplatinate, sodium chloroplatinate and platinum tetrachloride; the methylating agent is diethyl ether solution of methyl lithium, diethoxymethane solution of methyl lithium or toluene solution of trimethylaluminum.
3. The preparation method according to claim 1 or 2, wherein the organic solvent is one or more of diethyl ether, toluene, tetrahydrofuran, acetone and ethyl acetate.
4. A method according to claim 3, wherein the molar ratio of platinum halide to methylating agent is 1: 7-20; the mass volume ratio of the platinum halide to the organic solvent is 1g: 15-25 mL.
5. The method according to claim 1 or 4, wherein in step 1), the mixing time is 30 to 60 minutes, the mixing temperature is-18 to 0 ℃, and the reaction time is 10 to 14 hours;
when adding the methylation reagent, the temperature of the mixed solution is-18-0 ℃, and the time for adding the methylation reagent is 4-16 hours.
6. The method according to claim 5, wherein in step 2), the molar ratio of the 1, 2-dibromoethane to the platinum halide in step 1) is 3 to 7:1, the quenching reaction time is 0.5-1 h.
7. The method according to claim 6, wherein in the step 3), the mass ratio of the hydroiodic acid to the platinum halide in the step 1) is 0.4 to 0.8:1, the reaction time is 1-2 h.
8. The method according to claim 6 or 7, wherein the specific process of the post-treatment in step 3) is as follows: and sequentially performing spin drying, washing and filtering on the reaction liquid obtained by the reaction to obtain a crude product, and sequentially performing recrystallization, filtering and drying on the crude product to obtain the trimethyl platinum iodide crystal.
9. The trimethylplatinum iodide prepared by the preparation method of any one of claims 1 to 8.
10. Use of the trimethylplatinum iodide of claim 9 in the preparation of trimethylcyclopentadienyl platinum.
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| CN202311824005.1A CN117801026A (en) | 2023-12-27 | 2023-12-27 | Trimethyl platinum iodide and preparation method and application thereof |
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