CN117720586A - Amidino and cyclopentadienyl-containing magnesium compound and preparation method and application thereof - Google Patents
Amidino and cyclopentadienyl-containing magnesium compound and preparation method and application thereof Download PDFInfo
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- CN117720586A CN117720586A CN202311682234.4A CN202311682234A CN117720586A CN 117720586 A CN117720586 A CN 117720586A CN 202311682234 A CN202311682234 A CN 202311682234A CN 117720586 A CN117720586 A CN 117720586A
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- cyclopentadienyl
- amidino
- magnesium compound
- grignard reagent
- amidine
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- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 title claims abstract description 40
- 150000002681 magnesium compounds Chemical class 0.000 title claims abstract description 36
- 125000003739 carbamimidoyl group Chemical group C(N)(=N)* 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 29
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 18
- 150000001409 amidines Chemical class 0.000 claims abstract description 16
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 9
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000000231 atomic layer deposition Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000009835 boiling Methods 0.000 claims description 6
- NXPHGHWWQRMDIA-UHFFFAOYSA-M magnesium;carbanide;bromide Chemical compound [CH3-].[Mg+2].[Br-] NXPHGHWWQRMDIA-UHFFFAOYSA-M 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000000859 sublimation Methods 0.000 claims description 6
- 230000008022 sublimation Effects 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 5
- 230000006837 decompression Effects 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- IQSUNBLELDRPEY-UHFFFAOYSA-N 1-ethylcyclopenta-1,3-diene Chemical compound CCC1=CC=CC1 IQSUNBLELDRPEY-UHFFFAOYSA-N 0.000 claims description 3
- MWQKURVBJZAOSC-UHFFFAOYSA-N 1-propan-2-ylcyclopenta-1,3-diene Chemical compound CC(C)C1=CC=CC1 MWQKURVBJZAOSC-UHFFFAOYSA-N 0.000 claims description 3
- CDKFWIMBZAUBRS-UHFFFAOYSA-M [I-].CC[Mg+] Chemical compound [I-].CC[Mg+] CDKFWIMBZAUBRS-UHFFFAOYSA-M 0.000 claims description 3
- 239000004210 ether based solvent Substances 0.000 claims description 3
- CHDFNIZLAAFFPX-UHFFFAOYSA-N ethoxyethane;oxolane Chemical compound CCOCC.C1CCOC1 CHDFNIZLAAFFPX-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- VXWPONVCMVLXBW-UHFFFAOYSA-M magnesium;carbanide;iodide Chemical compound [CH3-].[Mg+2].[I-] VXWPONVCMVLXBW-UHFFFAOYSA-M 0.000 claims description 3
- NFWSQSCIDYBUOU-UHFFFAOYSA-N methylcyclopentadiene Chemical compound CC1=CC=CC1 NFWSQSCIDYBUOU-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- -1 solar energy Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012043 crude product Substances 0.000 description 8
- MHYQBXJRURFKIN-UHFFFAOYSA-N C1(C=CC=C1)[Mg] Chemical compound C1(C=CC=C1)[Mg] MHYQBXJRURFKIN-UHFFFAOYSA-N 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 125000000320 amidine group Chemical group 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 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 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000011825 aerospace material Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- UOSXPFXWANTMIZ-UHFFFAOYSA-N cyclopenta-1,3-diene;magnesium Chemical compound [Mg].C1C=CC=C1.C1C=CC=C1 UOSXPFXWANTMIZ-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Abstract
The invention relates to a magnesium compound containing amidine and cyclopentadienyl, a preparation method and application thereof, belonging to the technical field of organic synthesis. The structural formula of the amidine-and cyclopentadienyl-containing magnesium compound isWherein R is 1 、R 2 、R 3 Independently selected from hydrogen or C 1‑5 An alkyl group. The magnesium compound containing amidine and cyclopentadienyl is prepared by a Grignard reagent method, and based on the characteristics of stable Grignard reagent property, mature route and the like, the product meets the market demand, can be prepared in a large scale by using the Grignard reagent method, and greatly reduces the production cost.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a magnesium compound containing amidine groups and cyclopentadienyl groups, and a preparation method and application thereof.
Background
The related compound of cyclopentadienyl magnesium is an important compound for introducing cyclopentadienyl into transition metal, such as magnesium dicyclopentadiene, magnesium ethylidene and the like, in theory, the asymmetric cyclopentadienyl magnesium has the characteristic that an asymmetric cyclopentadienyl related ligand is introduced into the transition metal, according to theory, the asymmetric metal compound can greatly reduce the melting point of the compound and even enable the compound to achieve the liquefaction at room temperature due to the asymmetric structure characteristic of the compound, can better meet the technological requirement of atomic layer deposition, has wider application in the fields of new energy sources, aerospace materials, solar energy, semiconductor chips and the like, has great research potential in the research of other asymmetric compounds of transition metal, and has great scientific research and application prospect.
The method for preparing the cyclopentadienyl magnesium related compound in the prior art uses metal magnesium to directly react with cyclopentadiene and steam of derivatives thereof at high temperature, and only the cyclopentadienyl magnesium related compound with symmetrical uniformity can be prepared by the method, and the method is limited by the activity of the metal magnesium, so that the high-temperature and high-pressure auxiliary reaction is required, the reaction condition is harsh, the impurity content is high, and the large-scale industrial production is not facilitated.
Disclosure of Invention
In order to solve the technical problems, the invention provides an amidine and cyclopentadienyl-containing magnesium compound, a preparation method and application thereof, and a preparation method for preparing the amidine and cyclopentadienyl-containing magnesium compound by using a Grignard reagent method, which has the advantages of mild reaction conditions, high yield and high research value.
The first object of the present invention is to provide a magnesium compound containing amidine group and cyclopentadienyl group, the structure of which is as follows:
wherein R is 1 、R 2 、R 3 Independently selected from hydrogen or C 1-5 An alkyl group.
In one embodiment of the invention, the C 1-5 The alkyl group is selected from methyl (Me), ethyl (Et), n-propyl (n-Pr) or isopropyl (iPr).
A second object of the present invention is to provide a process for producing the amidine-and cyclopentadienyl-containing magnesium compound, comprising the steps of,
s1, adding cyclopentadiene monomers into a Grignard reagent solution under a protective atmosphere, and reacting to obtain a reaction solution;
s2, adding an amidino salt solution into the reaction solution in the step S1, and stirring for reaction to obtain a mixture;
s3, filtering, washing, decompressing, removing low boiling point, decompressing and sublimating the mixture of the S2 to obtain the magnesium compound containing amidine and cyclopentadienyl;
wherein the structural formula of the cyclopentadiene monomer is
The amidino salt has the structural formula
Wherein R is 1 And R is 2 Independently selected from hydrogen or C 1-5 An alkyl group;
R 3 selected from hydrogen or C 1-5 An alkyl group;
m is selected from one or more of Li, na and K.
In one embodiment of the present invention, in S1, the grignard reagent is selected from one or more of methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, and ethyl magnesium iodide.
Further, in S1, the grignard reagent is selected from methylmagnesium bromide and/or ethylmagnesium bromide.
In one embodiment of the invention, in S1, the solvent of the grignard reagent solution is selected from tetrahydrofuran and/or 2-methyltetrahydrofuran.
Further, in S1, the solvent of the grignard reagent solution is selected from 2-methyltetrahydrofuran.
In one embodiment of the present invention, in S1, the cyclopentadiene-based monomer is selected from one or more of cyclopentadiene (CpH), methylcyclopentadiene (MeCpH), ethylcyclopentadiene (EtCpH), isopropylcyclopentadiene (iPrCpH).
Further, in S1, the cyclopentadiene-based monomer is selected from cyclopentadiene (CpH).
In one embodiment of the present invention, in S1, the temperature of the reaction is room temperature (0 ℃ C. -30 ℃ C.) and may be any temperature between 0 ℃,1 ℃,2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃,7 ℃, 8 ℃, 9 ℃, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃,17 ℃, 18 ℃,19 ℃, 20 ℃,21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃,29 ℃, 30 ℃, or any two values.
In one embodiment of the present invention, in S2, the amidinate is selected from one or more of n-propylformamidinate, isopropylformamidinate, isopropylacetamimidinate and n-propylacetamimidinate.
Further, in S2, the amidinate is selected from lithium isopropylacetamidinate and/or sodium isopropylacetamidinate.
In one embodiment of the present invention, in S2, the solvent of the amidinate salt solution is selected from tetrahydrofuran ether solvents.
Further, in S2, the solvent of the amidinate salt solution is selected from tetrahydrofuran.
In one embodiment of the present invention, in S2, the temperature of the reaction is room temperature (0 ℃ to 30 ℃), which may be 0 ℃,1 ℃,2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃,7 ℃, 8 ℃, 9 ℃, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃,17 ℃, 18 ℃,19 ℃, 20 ℃,21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃,29 ℃, 30 ℃, or any temperature between any two values; the reaction time is 6h-10h, and can be 6.0h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h, 7.0h, 7.1h, 7.2h, 7.3h, 7.4h, 7.5h, 7.6h, 7.7h, 7.8h, 7.9h, 8.0h, 8.1h, 8.2h, 8.3h, 8.4h, 8.5h, 8.6h, 8.7h, 8.8h, 8.9h, 9.0h, 9.1h, 9.2h, 9.3h, 9.4h, 9.5h, 9.6h, 9.7h, 9.8h, 9.9h, 10.0h; or any time between any two values.
In one embodiment of the invention, the molar ratio of grignard reagent, cyclopentadiene monomer and amidinate salt is 1:1-1.2:1-1.2.
Further, the molar ratio of grignard reagent, cyclopentadiene monomer, and amidinate is (1:1:1), (1:1.1:1), (1:1:1.1), (1:1.1:1.1), (1:1.2:1), (1:1:1:1.2), (1:1.2:1.2), (1:1.1:1.2), and (1:1.2:1.1); or any point value between any two values.
Preferably, the molar ratio of grignard reagent, cyclopentadiene monomer and amidinate salt is 1:1.2:1.2.
in one embodiment of the present invention, in S3, the reduced pressure to remove low boiling adopts a temperature of 25 ℃ to 35 ℃; can be 25 ℃, 26 ℃, 27 ℃, 28 ℃,29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃; or any temperature between any two values. The temperature adopted by the decompression sublimation is 110-130 ℃; can be 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, 121 ℃, 122 ℃, 123 ℃, 124 ℃, 125 ℃, 126 ℃, 127 ℃, 128 ℃, 129 ℃, 130 ℃; or any temperature between any two values.
The third object of the present invention is to provide the use of said amidine-and cyclopentadienyl-containing magnesium compounds in atomic layer deposition processes.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The magnesium compound containing amidine and cyclopentadienyl is prepared by a Grignard reagent method, and the product meets the market demand based on the characteristics of stable Grignard reagent property, mature route and the like, can be prepared in a large scale by using the Grignard reagent method, and greatly reduces the production cost.
(2) The preparation method breaks the constraint that the traditional method can only prepare single magnesium related compounds, namely, can simultaneously connect cyclopentadienyl and amidino groups on the premise that the metal core is magnesium.
(3) In view of the characteristic that cyclopentadienyl magnesium can help transition metal to introduce cyclopentadienyl, the prepared magnesium compound containing amidine and cyclopentadienyl can provide scientific thinking for introducing asymmetric groups to other transition metals in the future.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a process for preparing isopropylacetamido cyclopentadienyl magnesium prepared in example 1 of the present invention;
FIG. 2 is a nuclear magnetic spectrum of isopropylacetamido cyclopentadienyl magnesium prepared in example 1 of the present invention;
FIG. 3 is a graph of ALD (atomic layer deposition) thickness versus cycle number for isopropylacetamido cyclopentadienyl magnesium prepared in example 1 of the present invention.
Detailed Description
In order to solve the technical problems, the invention provides an amidine and cyclopentadienyl-containing magnesium compound, a preparation method and application thereof, and a preparation method for preparing the amidine and cyclopentadienyl-containing magnesium compound by using a Grignard reagent method, which has the advantages of mild reaction conditions, high yield and high research value.
The first object of the present invention is to provide a magnesium compound containing amidine group and cyclopentadienyl group, the structure of which is as follows:
wherein R is 1 、R 2 、R 3 Independently selected from hydrogen or C 1-5 An alkyl group.
In one embodiment of the invention, the C 1-5 The alkyl group is selected from methyl (Me), ethyl (Et), n-propyl (n-Pr) or isopropyl (iPr).
Further, R 1 Is isopropyl (iPr), R 2 Methyl (Me), R 3 H.
A second object of the present invention is to provide a process for producing the amidine-and cyclopentadienyl-containing magnesium compound, comprising the steps of,
s1, adding cyclopentadiene monomers into a Grignard reagent solution under a protective atmosphere, and reacting to obtain a reaction solution;
s2, adding an amidino salt solution into the reaction solution in the step S1, and stirring for reaction to obtain a mixture;
s3, filtering, washing, decompressing, removing low boiling point, decompressing and sublimating the mixture of the S2 to obtain the magnesium compound containing amidine and cyclopentadienyl;
wherein the structural formula of the cyclopentadiene monomer is
The amidino salt has the structural formula
Wherein R is 1 And R is 2 Independently selected from hydrogen or C 1-5 An alkyl group;
R 3 selected from hydrogen or C 1-5 An alkyl group;
m is selected from one or more of Li, na and K.
In one embodiment of the invention, since the reaction raw materials and products are all liable to react with water, oxygen, etc., the whole preparation process is carried out under a protective atmosphere, and the raw materials and target products are protected from being damaged by any water and oxygen in the reaction system.
Further, the protective atmosphere includes, but is not limited to, nitrogen atmosphere, inert gas atmosphere.
Preferably, the protective atmosphere is a nitrogen atmosphere.
In one embodiment of the present invention, in S1, the grignard reagent is selected from one or more of methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide, and ethyl magnesium iodide.
Further, in S1, the grignard reagent is selected from methylmagnesium bromide and/or ethylmagnesium bromide.
In one embodiment of the invention, in S1, the solvent of the grignard reagent solution is selected from tetrahydrofuran and/or 2-methyltetrahydrofuran, the solvent acting to dissolve the reactants and products and to increase the activity of the starting materials and promote the reaction.
Further, in S1, the solvent of the grignard reagent solution is selected from 2-methyltetrahydrofuran.
In one embodiment of the present invention, in S1, the cyclopentadiene-based monomer is selected from one or more of cyclopentadiene (CpH), methylcyclopentadiene (MeCpH), ethylcyclopentadiene (EtCpH), isopropylcyclopentadiene (iPrCpH).
Further, in S1, the cyclopentadiene-based monomer is selected from cyclopentadiene (CpH).
In one embodiment of the present invention, in S1, the temperature of the reaction is room temperature (0 ℃ C. -30 ℃ C.) and may be any temperature between 0 ℃,1 ℃,2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃,7 ℃, 8 ℃, 9 ℃, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃,17 ℃, 18 ℃,19 ℃, 20 ℃,21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃,29 ℃, 30 ℃, or any two values.
In one embodiment of the present invention, in S2, the amidinate is selected from one or more of n-propylformamidinate, isopropylformamidinate, isopropylacetamimidinate and n-propylacetamimidinate.
Further, in S2, the amidinate is selected from lithium isopropylacetamidinate and/or sodium isopropylacetamidinate.
In one embodiment of the present invention, in S2, the solvent of the amidinate salt solution is selected from tetrahydrofuran ether solvents, the solvent functions to dissolve the reactants and products, and to enhance the activity of the raw materials, promoting the reaction.
Further, in S2, the solvent of the amidinate salt solution is selected from tetrahydrofuran.
In one embodiment of the present invention, in S2, the temperature of the reaction is room temperature (0 ℃ to 30 ℃), which may be 0 ℃,1 ℃,2 ℃, 3 ℃, 4 ℃, 5 ℃, 6 ℃,7 ℃, 8 ℃, 9 ℃, 10 ℃, 11 ℃, 12 ℃, 13 ℃, 14 ℃, 15 ℃, 16 ℃,17 ℃, 18 ℃,19 ℃, 20 ℃,21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃,29 ℃, 30 ℃, or any temperature between any two values; the reaction time is 6h-10h, and can be 6.0h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h, 7.0h, 7.1h, 7.2h, 7.3h, 7.4h, 7.5h, 7.6h, 7.7h, 7.8h, 7.9h, 8.0h, 8.1h, 8.2h, 8.3h, 8.4h, 8.5h, 8.6h, 8.7h, 8.8h, 8.9h, 9.0h, 9.1h, 9.2h, 9.3h, 9.4h, 9.5h, 9.6h, 9.7h, 9.8h, 9.9h, 10.0h; or any time between any two values.
In one embodiment of the invention, the molar ratio of grignard reagent, cyclopentadiene monomer and amidinate salt is 1:1-1.2:1-1.2.
Further, the molar ratio of grignard reagent, cyclopentadiene monomer, and amidinate is (1:1:1), (1:1.1:1), (1:1:1.1), (1:1.1:1.1), (1:1.2:1), (1:1:1:1.2), (1:1.2:1.2), (1:1.1:1.2), and (1:1.2:1.1); or any point value between any two values.
Preferably, the molar ratio of grignard reagent, cyclopentadiene monomer and amidinate salt is 1:1.2:1.2.
in one embodiment of the present invention, in S3, the reduced pressure to remove low boiling adopts a temperature of 25 ℃ to 35 ℃; can be 25 ℃, 26 ℃, 27 ℃, 28 ℃,29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃; or any temperature between any two values. The temperature adopted by the decompression sublimation is 110-130 ℃; can be 110 ℃, 111 ℃, 112 ℃, 113 ℃, 114 ℃, 115 ℃, 116 ℃, 117 ℃, 118 ℃, 119 ℃, 120 ℃, 121 ℃, 122 ℃, 123 ℃, 124 ℃, 125 ℃, 126 ℃, 127 ℃, 128 ℃, 129 ℃, 130 ℃; or any temperature between any two values.
Further, the decompression sublimation is divided into two stages, wherein the first stage is to decompress and sublimate the residue after removing low boiling point, and collect white solid which is crude product containing a small amount of excessive lithium isopropylacetamido; the second stage is to sublimate the crude product under reduced pressure, and discard the front cut fraction to obtain pure magnesium compound containing amidine and cyclopentadienyl.
In one embodiment of the present invention, in S3, the washed solvent is selected from one or more of toluene, diethyl ether and tetrahydrofuran.
In one embodiment of the invention, isopropyl acetamido cyclopentadienyl magnesium is prepared by taking Grignard reagent ethyl magnesium bromide (EtMgBr), monomer cyclopentadiene (CpH) and amidinate isopropyl acetamido lithium (iPr-AMDLi) as reactants, and the reaction equation is as follows:
the third object of the present invention is to provide the use of said amidine-and cyclopentadienyl-containing magnesium compounds in atomic layer deposition processes.
The present invention will be further described in conjunction with the drawings and the detailed embodiments so that those skilled in the art may better understand and practice the invention and it is evident that the described embodiments are only some, but not all, of the embodiments of the invention. It should be understood that the detailed description is intended to illustrate the invention, but is not intended to limit the invention to the particular embodiments disclosed.
In the present invention, unless otherwise defined, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In the present invention, the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items, unless otherwise indicated.
In the present invention, unless otherwise indicated, the terms "upper," "lower," "front," "rear," "inner," "outer," and the like are used herein without regard to the orientation or positional relationship shown in the drawings, merely to facilitate the description of the present application and to simplify the description, and do not denote or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus should not be construed as limiting the invention. Furthermore, the terms "first," "second," and the like, herein, are used for distinguishing between different elements and not necessarily for describing a sequential or chronological order, and not for limiting that "first" and "second" are of different types.
In the present invention, unless otherwise indicated, all the experimental methods used in the examples of the present invention are conventional methods, and materials, reagents and the like used, unless otherwise indicated, are commercially available.
In the present application, unless otherwise indicated, the terms "comprises" and/or "comprising" when used in the present specification specify the presence of stated features, integers, steps, operations, elements, or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or groups thereof.
Example 1
Referring to FIG. 1, the amidine and cyclopentadienyl-containing magnesium compound and the preparation method thereof specifically comprise the following steps:
a solution of ethyl magnesium bromide in 2-methyltetrahydrofuran (3.4 mol/L,29.4 mL) was charged into a 250mL reaction flask under nitrogen, freshly depolymerized cyclopentadiene (0.12 mol,7.93 g) was injected into the reaction flask using a syringe at room temperature under stirring, an excess of lithium isopropylacetamido (0.12 mol,17.78 g) in tetrahydrofuran was added to the reaction system at room temperature to give a white precipitate, after stirring for 8 hours, filtration, toluene washing, collecting the filtrate, removing the solvent under reduced pressure at 30℃and sublimating the crude product out at 120℃to give a white solid, which was further sublimated to give the white solid lithium isopropylacetamido cyclopentadienyl magnesium in 82% yield.
The sample was characterized by nuclear magnetism, and the results are shown in fig. 2: 1 HNMR(500MHz,C 6 D 6 )d(ppm):1.05(d,12H,CH 3 ),1.62(s,3H，CH3),3.20(m,2H,CH),6.22(s,5H,ArH).
purity of metal: 5N.
Example 2
The invention relates to a magnesium compound containing amidine and cyclopentadienyl and a preparation method thereof, which specifically comprises the following steps:
under the protection of nitrogen, a 2-methyltetrahydrofuran solution (3.4 mol/L,29.4 mL) of ethylmagnesium bromide was added to a 250mL reaction flask, fresh depolymerized cyclopentadiene (0.12 mol,7.9 g) was injected into the reaction flask with a syringe at room temperature under stirring, an excessive tetrahydrofuran solution of sodium isopropylacetamido (0.12 mol,19.71 g) was introduced into the reaction system at room temperature to generate a white precipitate, after stirring for 8 hours, filtration, toluene washing, filtrate collection, removal of the solvent under reduced pressure at 30℃and sublimation of the crude product at 120℃to obtain a white solid, and the crude product was further sublimated to obtain a white solid of sodium isopropylacetamido cyclopentadienyl magnesium in 78% yield.
Example 3
The invention relates to a magnesium compound containing amidine and cyclopentadienyl and a preparation method thereof, which specifically comprises the following steps:
a solution of methyl magnesium bromide in 2-methyltetrahydrofuran (3.4 mol/L,29.4 mL) was charged into a 250mL reaction flask under nitrogen, freshly depolymerized cyclopentadiene (0.12 mol,7.9 g) was injected into the reaction flask at room temperature with stirring, an excess of sodium isopropylacetamido (0.12 mol,19.71 g) in tetrahydrofuran was introduced into the reaction system at room temperature to give a white precipitate, after stirring for 8h, filtration, washing with toluene, collecting the filtrate, removing the solvent under reduced pressure at 30℃and sublimating the crude product at 120℃to give a white solid, which was further sublimated to give a white solid sodium isopropylacetamido cyclopentadienyl in 78% yield.
Example 4
The invention relates to a magnesium compound containing amidine and cyclopentadienyl and a preparation method thereof, which specifically comprises the following steps:
under the protection of nitrogen, a 2-methyltetrahydrofuran solution (3.4 mol/L,29.4 mL) of ethylmagnesium bromide was added to a 250mL reaction flask, fresh depolymerized cyclopentadiene (0.12 mol,7.9 g) was injected into the reaction flask with a syringe at room temperature under stirring, an excessive amount of a tetrahydrofuran solution of potassium isopropylacetamido (0.12 mol,21.76 g) was introduced into the reaction system at room temperature to generate a white precipitate, after stirring for 8 hours, filtration, toluene washing, filtrate collection, removal of the solvent under reduced pressure at 30℃and sublimation of the crude product at 120℃to obtain a white solid, and the crude product was further sublimated to obtain a white solid of potassium isopropylacetamido cyclopentadienyl magnesium in 75% yield.
Application example
Atomic layer deposition of the isopropylacetamido cyclopentadienyl magnesium sample resulted in the following:
the isopropylacetamido cyclopentadienyl magnesium obtained in example 1 can be reacted with H at a deposition temperature of 150-300 DEG C 2 O、H 2 O 2 、O 3 、O 2 The reaction of plasma, alcohols and the like occurs, the refractive index is 1.67-1.75, the deposition rate is 0.088 nm/cycle-0.11 nm/cycle, and the carbon content is less than 3at%. The results of the deposition thickness versus cycle number graph are shown in fig. 3, and it can be seen from fig. 3 that the sample has good linear growth characteristics and the sample has very good stability.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A magnesium compound containing amidino and cyclopentadienyl, characterized by the following structure:
wherein R is 1 、R 2 、R 3 Independently selected from hydrogen or C 1-5 An alkyl group.
2. The amidino-and cyclopentadienyl-containing magnesium compound according to claim 1, wherein said C 1-5 The alkyl group is selected from methyl, ethyl, n-propyl or isopropyl.
3. A process for producing an amidino-and cyclopentadienyl-containing magnesium compound according to claim 1 or 2, comprising the steps of,
s1, adding cyclopentadiene monomers into a Grignard reagent solution under a protective atmosphere, and reacting to obtain a reaction solution;
s2, adding an amidino salt solution into the reaction solution in the step S1, and stirring for reaction to obtain a mixture;
s3, filtering, washing, decompressing, removing low boiling point, decompressing and sublimating the mixture of the S2 to obtain the magnesium compound containing amidine and cyclopentadienyl;
wherein the structural formula of the cyclopentadiene monomer is
The amidino salt has the structural formula
Wherein R is 1 And R is 2 Independently selected from hydrogen or C 1-5 An alkyl group;
R 3 selected from hydrogen or C 1-5 An alkyl group;
m is selected from one or more of Li, na and K.
4. The method for producing an amidino-and cyclopentadienyl-containing magnesium compound according to claim 3, wherein in S1, the grignard reagent is one or more selected from the group consisting of methyl magnesium bromide, methyl magnesium iodide, ethyl magnesium bromide and ethyl magnesium iodide.
5. The process for producing an amidine-and cyclopentadienyl-containing magnesium compound according to claim 3, wherein in S1, the solvent of the grignard reagent solution is selected from tetrahydrofuran and/or 2-methyltetrahydrofuran.
6. The method for producing an amidine-and cyclopentadienyl-containing magnesium compound according to claim 3, wherein in S1, the cyclopentadiene-based monomer is one or more selected from cyclopentadiene, methylcyclopentadiene, ethylcyclopentadiene and isopropylcyclopentadiene.
7. The method for producing an amidino-and cyclopentadienyl-containing magnesium compound according to claim 3, wherein in S2, the amidino salt is selected from one or more of n-propylformamidinate, isopropylformamidinate, isopropylacetamimidinate and n-propylacetamimidinate; the solvent of the amidino salt solution is selected from tetrahydrofuran ether solvents.
8. The method for producing an amidino-and cyclopentadienyl-containing magnesium compound according to claim 3, wherein the molar ratio of said grignard reagent, cyclopentadiene monomer and amidino salt is 1:1-1.2:1-1.2.
9. The process for producing an amidino-and cyclopentadienyl-containing magnesium compound according to claim 3, wherein in S3, the reduced pressure is used at a temperature of 25 to 35 ℃; the temperature adopted by the decompression sublimation is 110-130 ℃.
10. Use of the amidine-and cyclopentadienyl-containing magnesium compounds according to claim 1 or 2 in atomic layer deposition processes.
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