CN111606950A - Method for synthesizing silicon-based phosphorus cluster compound and product thereof - Google Patents
Method for synthesizing silicon-based phosphorus cluster compound and product thereof Download PDFInfo
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- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 150000001875 compounds Chemical class 0.000 title claims abstract description 15
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 15
- 239000010703 silicon Substances 0.000 title claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 12
- 239000011574 phosphorus Substances 0.000 title claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000011261 inert gas Substances 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 239000002798 polar solvent Substances 0.000 claims abstract description 9
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 claims abstract description 5
- 150000004756 silanes Chemical class 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 26
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 25
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 19
- 239000011734 sodium Substances 0.000 claims description 17
- 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 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 239000012454 non-polar solvent Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 6
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 150000003017 phosphorus Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- 239000012043 crude product Substances 0.000 description 10
- 229910000799 K alloy Inorganic materials 0.000 description 7
- 239000003495 polar organic solvent Substances 0.000 description 6
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 238000004983 proton decoupled 13C NMR spectroscopy Methods 0.000 description 5
- 238000004679 31P NMR spectroscopy Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910000528 Na alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- BTVWZWFKMIUSGS-UHFFFAOYSA-N dimethylethyleneglycol Natural products CC(C)(O)CO BTVWZWFKMIUSGS-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- DHNUAKOQUGJUGA-UHFFFAOYSA-N silicon;sulfane Chemical compound [Si].S DHNUAKOQUGJUGA-UHFFFAOYSA-N 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6561—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing systems of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring or ring system, with or without other non-condensed hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
The invention discloses a method for synthesizing a silicon-based phosphorus cluster compound, which comprises the following steps: (1) under the protection of inert gas, adding a polar solvent, a metal reducing agent M, red phosphorus and a catalyst into a reactor, and stirring and heating for reaction; (2) cooling the reaction system obtained in the step (1) and maintaining the temperature below-20 ℃, adding halogenated silane, naturally heating to room temperature and continuing to react, and carrying out post-treatment after the reaction is finished to obtain a product shown as the following formula (I);
wherein Silyl represents the formula R1R2R3Si，R1、R2、R3The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl. The invention also discloses a silicon-based phosphorus cluster compound synthesized by the method.
Description
Technical Field
The invention relates to the technical field of organic silicon, in particular to a method for synthesizing a silicon-based phosphorus cluster compound and a product thereof.
Background
P7R3The compound is a compound which has a plurality of P centers to form an inorganic cage-shaped inner core and is substituted by organic functional groups at the periphery. When R is silicon base, the compound has good stability and organic solvent solubility, can be used for constructing functional group inorganic phosphorus cluster derivatives with other topological structures, and is expected to be used as a precursor for preparing catalysts and nano materials. (Angew. chem. ed. Engl.,1981,20, 33; Angew. chem. Ed. Engl.,1982,21,863) although this class of compounds has been studied for many years, its preparation process is not perfect and its functional group derivatives are of very limited variety, affecting its popularization in the fields of synthetic chemistry and material chemistry.
The traditional preparation method of the compound is (taking P as the raw material)7(SiMe3)3For example): formation of liquid alloys with white phosphorus (P) in ether solvents such as dimethyl glycol ether (DME) with sodium and potassium metals4) Reaction to produce M3P7Then, further reacting with trimethylchlorosilane (Me)3SiCl) to obtain the product. (Z.anorg. allg.chem.1978,440,171) the reaction formula is shown below:
this method has significant drawbacks, such as: 1) the reducing agent in the system is active sodium-potassium alloy, so that the system is easy to catch fire or explode and has higher danger; 2) the use of toxic and flammable white phosphorus as a source of phosphorus is hazardous.
Schmidbaur et al improved the preparation method by replacing white phosphorus with cheap and readily available red phosphorus and replacing DME with toluene, instead of the nonpolar solvent, to perform the silylation reaction, and obtain the product P in higher yield7(SiMe3)3。(Phosphorus,Sulfur Silicon Relat.Elem.1995,102,217-219)
However, this method still has drawbacks, such as: 1) the reducing agent sodium-potassium alloy used in the system still has higher danger; 2) the reaction time is long, and the steps are more; 3) drying under reduced pressure halfway to obtain M3P7The (M ═ Na, K) salts mix with large amounts of unreacted sodium potassium alloy and form larger solidsAgglomeration requires manual pulverization under an inert atmosphere. These all impose limitations on practical operation.
Most of the compounds reported at present are trimethylsilyl-substituted P7 3-Clusters, other different silicon-based functional groups (-SiR)3) The derivatives of (a) have not been developed. Only Hassler et al have reported the preparation of P by a silicon-based exchange reaction7(SiPh3)3(Angew. chem.1982,94,869) and incomplete substitution products [ (Me)3Si)3Si]2P7(SiMe3)。(J.Organomet.Chem.,2011,696,652)
Disclosure of Invention
Based on the above reasons, the invention provides a method for synthesizing silicon-based phosphorus cluster compound, and the silicon-based phosphorus cluster compound is prepared by continuous reaction in a one-pot method, has universality, is shorter, efficient, safe and feasible compared with the traditional method.
A method of synthesizing silicon-based phosphorus clusters comprising the steps of:
(1) under the protection of inert gas, adding a polar solvent, a metal reducing agent M, red phosphorus and a catalyst into a reactor, and stirring and heating for reaction;
(2) cooling the reaction system obtained in the step (1) and maintaining the temperature below-20 ℃, adding halogenated silane, naturally heating to room temperature and continuing to react, and carrying out post-treatment after the reaction is finished to obtain a product shown as the following formula (I);
wherein Silyl represents the formula R1R2R3Si，R1、R2、R3The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl. The saturated alkyl group may be a methyl group, an ethyl group, a propyl group, etc., the unsaturated alkyl group may be a vinyl group, an allyl group, etc., the alkoxy group may be a methoxy group, an ethoxy group, etc., and the aryl group may be a phenyl group, a substituted phenyl group, etc.
The inert gas in the present invention may be at least one of nitrogen gas and rare gas, and the rare gas may be argon gas or the like.
In the step (1), the polar solvent may be one commonly used in the art, and specifically may be at least one of dimethyl glycol ether (DME), propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, tetrahydrofuran, 2-methyl-tetrahydrofuran, and 1, 4-dioxane. The polar solvent is preferably DME.
In the step (1), the metal reducing agent M may be a metal reducing agent commonly used in the art, and specifically may be at least one of lithium, sodium, and potassium, or an alloy containing at least one of lithium, sodium, and potassium, such as a sodium-potassium alloy. The metal reducing agent M is preferably Na.
In the step (1), the catalyst is at least one of naphthalene, 1-methylnaphthalene and 2-methylnaphthalene, and naphthalene is preferred. The molar ratio of the addition amount of the catalyst to the addition amount of the red phosphorus is preferably 1-6: 100.
One preferable substance combination of the reaction system in the step (1) is as follows: the polar solvent is DME, the metal reducing agent M is Na, and the catalyst is naphthalene. The obtained product has the highest purity and the method is the safest.
In the step (1), the heating temperature can be adjusted according to the actual reflux condition, and is preferably 60-130 ℃.
In the step (1), the reaction time is only 3-18 h.
The general formula of the halogenated silane is R1R2R3SiX, wherein R1、R2、R3The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl, and X is halogen such as F, Cl, Br, I and the like. The saturated alkyl group may be a methyl group, an ethyl group, a propyl group, etc., the unsaturated alkyl group may be a vinyl group, an allyl group, etc., the alkoxy group may be a methoxy group, an ethoxy group, etc., and the aryl group may be a phenyl group, a substituted phenyl group, etc.
Preferably, R in Silyl1、R2、R3The carbon number of the groups is 1-12 independently. Preferably, R in the halosilane1、R2、R3The carbon number of the groups is 1-12 independently.
Preferably, the molar ratio of the metal reducing agent M to the red phosphorus to the halogenated silane is 3:7: 3-5.
In the step (2), the cooling temperature is preferably-78 to-20 ℃.
In the step (2), the continuous reaction time is only 0.5-2 h.
In the step (2), the post-treatment is preferably: filtering and collecting filtrate under the protection of inert gas, removing the solvent under reduced pressure, and finally washing by a non-polar solvent to obtain the product.
The nonpolar solvent is preferably an alkane and/or cycloalkane, and the nonpolar solvent is preferably one having a carbon number of not less than 6. The non-polar solvent can be hexane, pentane, heptane, cyclohexane and the like, and is preferably cyclohexane, and the purity of the obtained product is highest.
The invention also provides a silicon-based phosphorus cluster compound synthesized by the method.
Compared with the prior art, the invention has the main advantages that: compared with the traditional method, the method disclosed by the invention has the advantages that a proper metal reducing agent, a polar solvent and a catalyst are selected, a special synthesis method is combined, a good synergistic effect is exerted, and the effects of few steps, safety in operation, high reaction efficiency, high product purity, good product group universality and the like are achieved.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
(1) Under the protection of inert gas, DME (500mL), metallic sodium (0.55mol,12.7g), red phosphorus (1.29mol, 40g) and naphthalene (0.038mol, 4.9g) are added into a 1L reaction bottle and stirred and heated for 8 hours; (2) the reaction system was cooled to-78 ℃ and Me was added while maintaining this low temperature3SiCl (0.66mol,71.9g), naturally heating to room temperature and continuing to react for 2 hours; (3) after the reaction is finished, filtering and collecting filtrate under the protection of inert gas, and removing the solvent under reduced pressure to obtain a crude product;(4) washing the crude product with n-hexane to obtain a pure product P7(SiMe3)3(62.3g), yield 78.1%.
Nuclear magnetic characterization was as follows:1H NMR(400MHz,C6D6,298K,ppm):＝0.21(s,9H,-CH3).13C{1H}NMR(400MHz,C6D6,298K,ppm):＝3.1(SiC).29Si(400MHz,C6D6,298K,ppm)＝7.1.31P(400MHz,C6D6,298K,ppm)＝13.16(m,3P,P234),-85.36(qq,1P,P1),-142.41(m,3P,P567).
example 2
(1) Under the protection of inert gas, DME (500mL), metallic sodium (0.55mol,12.7g), red phosphorus (1.29mol, 40g) and naphthalene (0.038mol, 4.9g) are added into a 1L reaction bottle and stirred and heated for 8 hours; (2) the reaction was cooled to-78 ℃ and the low temperature was maintained and Ph was added3SiCl (0.66mol,194.6g), naturally heating to room temperature and continuing to react for 2 hours; (3) after the reaction is finished, filtering and collecting filtrate under the protection of inert gas, and removing the solvent under reduced pressure to obtain a crude product; (4) washing the crude product with n-hexane to obtain a pure product P7(SiPh3)3(131.3g), yield 72.4%.
Nuclear magnetic characterization was as follows:1H NMR(400MHz,C6D6,298K,ppm):＝7.37-7.46(m,45H,-PhH).13C{1H}NMR(400MHz,C6D6,298K,ppm):＝129.5,130.5,132.5(-phC).29Si NMR(400MHz,C6D6,298K,ppm)＝4.2.31P NMR(400MHz,C6D6,298K,ppm)＝12.06(m,3P,P234),-82.26(qq,1P,P1),-121.32(m,3P,P567).
example 3
(1) Under the protection of inert gas, DME (500mL), metallic sodium (0.55mol,12.7g), red phosphorus (1.29mol, 40g) and naphthalene (0.038mol, 4.9g) are added into a 1L reaction bottle and stirred and heated for 8 hours; (2) the reaction system was cooled to-78 ℃ and PhMe was added while maintaining this low temperature2SiCl (0.66mol,112.7g), naturally heating to room temperature and continuing to react for 2 hours; (3) after the reaction is finished, filtering and collecting filtrate under the protection of inert gas, and removing the solvent under reduced pressure to obtain a crude product; (4) washing the crude product with n-hexane to obtain a pure product P7(SiMe2Ph)3(79.8g), yield 70.2%.
Nuclear magnetic characterization was as follows:1H NMR(400MHz,C6D6,298K,ppm):＝7.18-7.17(s,15H,-PhH),0.66(s,36H,-SiMe2).13C{1H}NMR(400MHz,C6D6,298K,ppm):＝129.5，130.0，132.5，133.0(-PhC),2.8(SiMe).29Si NMR(400MHz,C6D6,298K,ppm)＝7.01.31P NMR(400MHz,C6D6,298K,ppm)：＝13.06(m,3P,P234),-84.26(qq,1P,P1),-139.32(m,3P,P567).
example 4
(1) Under the protection of inert gas, DME (500mL), metallic sodium (0.55mol,12.7g), red phosphorus (1.29mol, 40g) and naphthalene (0.038mol, 4.9g) are added into a 1L reaction bottle and stirred and heated for 8 hours; (2) the reaction was cooled to-78 ℃ and the addition (iPrO) was maintained at this low temperature3SiCl (0.66mol,158.9g), naturally heating to room temperature and continuing to react for 2 hours; (3) after the reaction is finished, filtering and collecting filtrate under the protection of inert gas, and removing the solvent under reduced pressure to obtain a crude product; (4) washing the crude product with n-hexane to obtain a pure product P7[Si(iPrO)3]3(116.5g), yield 76.3%.
Nuclear magnetic characterization was as follows:1H NMR(400MHz,C6D6,298K,ppm):＝3.02-309.(m,9H,iPrH),1.22(d,54H,iPrMe).13C{1H}NMR(400MHz,C6D6,298K,ppm):＝61.7(-OC),28.3(iPrMe-C).29SiNMR(400MHz,C6D6,298K,ppm)＝5.3.31P NMR(400MHz,C6D6,298K,ppm)＝15.06(m,3P,P234),-87.26(qq,1P,P1),-150.32(m,3P,P567).
example 5
(1) Under the protection of inert gas, DME (500mL), metallic sodium (0.55mol,12.7g), red phosphorus (1.29mol, 40g) and naphthalene (0.038mol, 4.9g) are added into a 1L reaction bottle and stirred and heated for 8 hours; (2) the reaction was cooled to-78 ℃ and (CH) was added while maintaining the low temperature2＝CH)3SiCl (0.66mol,95.5g), naturally heating to room temperature and continuing to react for 2 hours; (3) after the reaction is finished, filtering and collecting filtrate under the protection of inert gas, and removing the solvent under reduced pressure to obtain a crude product; (4) washing the crude product with n-hexane to obtain a pure product P7[Si(CH＝CH2)3]3(67.9g), yield 68.0%.
Nuclear magnetic characterization was as follows:1H NMR(400MHz,C6D6,298K,ppm):＝5.67-5.73(m,18H,＝CH2),5.21-5.26(m,9H,＝CH-Si).13C{1H}NMR(400MHz,C6D6,298K,ppm):＝138.0(＝CH2),124.9(＝CH-Si).29Si NMR(400MHz,C6D6,298K,ppm)＝8.4.31P NMR(400MHz,C6D6,298K,ppm):＝14.06(m,3P,P234),-86.26(qq,1P,P1),-141.32(m,3P,P567).
examples 6 to 35
Investigating polar solvents
Examples 6 to 10: the following examples 6 to 10 were obtained with yields of 52.4%, 52.0%, 51.8%, 52.2% and 52.4% respectively, except that the polar organic solvent in examples 1 to 5 was replaced with dimethyl glycol ether.
Examples 11 to 15: the same procedure was followed except that the polar organic solvent in examples 1 to 5 was replaced with propylene glycol diethyl ether instead of dimethyl glycol ether, respectively, to obtain examples 11 to 15 in the yields of 55.4%, 54.6%, 52.0%, 55.0%, and 55.1%, respectively.
Examples 16 to 20: the procedures were not changed except that the polar organic solvent in examples 1 to 5 was replaced with propylene glycol dibutyl ether by dimethyl glycol ether, respectively, to obtain examples 16 to 20, and the yields of the obtained products were 46.5%, 45.5%, 44.1%, 45.0%, and 49.1%, respectively.
Examples 21 to 25: the following examples 21 to 25 were obtained with yields of 60.2%, 59.3%, 57.8%, 60.0% and 63.1% respectively, except that the polar organic solvent in examples 1 to 5 was replaced with a different solvent such as dimethylethylene glycol ether.
Examples 26 to 30: the following examples 26 to 30 were obtained with yields of 51.2%, 50.3%, 48.9%, 51% and 54.1% respectively, except that the polar organic solvent in examples 1 to 5 was replaced with dimethyl glycol ether and 2-methyl-tetrahydrofuran, respectively.
Examples 31 to 35: the following examples 31-35 were obtained with yields of 37.2%, 36.9%, 37%, 36.8%, and 38.0% respectively, except that the polar organic solvent in examples 1-5 was replaced with 1, 4-dioxane, respectively, and dimethyl glycol ether.
The results are shown in Table 1.
TABLE 1
It can be seen that the dimethyl glycol ether has the best effect and the highest yield in the method and the reaction system of the invention.
Examples 36 to 50
Investigating metal reducing agents
Examples 36 to 40: except for replacing potassium by sodium in the metal reducing agent in the step (1) in the embodiments 1 to 5, the other operations are not changed, so that the embodiments 36 to 40 are obtained, and the product yield is 61.0%, 60.8%, 59.7%, 60.0% and 56.5% in sequence.
Examples 41 to 45: except for replacing the metal reducing agent in the step (1) of the embodiment 1 to 5 by lithium from sodium, other operations are unchanged, so that the embodiments 41 to 45 are obtained, and the product yield is 57.4%, 56.8%, 55.0%, 58.3% and 53.7% in sequence.
Examples 45 to 50: except for replacing the metal reducing agent in the step (1) of the embodiment 1 to 5 by sodium and potassium alloy, other operations are unchanged, so that the embodiments 45 to 50 are obtained, and the product yield is 69.0%, 68.8%, 65.2%, 63.0% and 63.9% in sequence.
The results are shown in Table 2.
TABLE 2
It is seen that, although the sodium-potassium alloy is preferable, the sodium-potassium alloy is highly dangerous. Therefore, when only single metal sodium is used as the metal reducing agent, the yield is high, and the safety is good.
Examples 51 to 65
Investigating catalyst
Examples 51 to 55: the operation was not changed except that the catalysts in step (1) of examples 1 to 5 were changed from naphthalene to no catalyst, thereby obtaining examples 51 to 55 with product yields of 23.5%, 23.1%, 23.0%, 23.8% and 21.0% in this order.
Examples 56 to 60: the catalysts of the step (1) of examples 1 to 5 were changed from naphthalene to 1-methylnaphthalene, but the other operations were not changed to obtain examples 56 to 60, and the yields of the obtained products were 45.7%, 44.5%, 42.9%, 46.0% and 42.3% in this order.
Examples 61 to 65: the catalysts of the step (1) of examples 1 to 5 were changed from naphthalene to 2-methylnaphthalene, but the other operations were not changed to obtain the products of examples 61 to 65, and the yields of the obtained products were 50.3%, 49.9%, 47.6%, 48.0% and 44.5% in this order.
The results are shown in Table 3.
TABLE 3
Therefore, the method and the reaction system have the best effect of naphthalene as a catalyst and have the highest yield.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A method for synthesizing silicon-based phosphorus clusters, comprising the steps of:
(1) under the protection of inert gas, adding a polar solvent, a metal reducing agent M, red phosphorus and a catalyst into a reactor, and stirring and heating for reaction;
(2) cooling the reaction system obtained in the step (1) and maintaining the temperature below-20 ℃, adding halogenated silane, naturally heating to room temperature and continuing to react, and carrying out post-treatment after the reaction is finished to obtain a product shown as the following formula (I);
wherein Silyl represents the formula R1R2R3Si，R1、R2、R3The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl.
2. The method according to claim 1, wherein in the step (1), the polar solvent is at least one of dimethyl glycol ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, tetrahydrofuran, 2-methyl-tetrahydrofuran, and 1, 4-dioxane;
the metal reducing agent M is at least one of lithium, sodium and potassium or an alloy containing at least one of lithium, sodium and potassium;
the catalyst is at least one of naphthalene, 1-methylnaphthalene and 2-methylnaphthalene, and the molar ratio of the addition amount of the catalyst to the addition amount of red phosphorus is 1-6: 100.
3. The method according to claim 1 or 2, wherein in the step (1), the heating temperature is 60 to 130 ℃, and the reaction time is 3 to 18 hours.
4. The method of claim 1, wherein the halosilane has the formula R1R2R3SiX, wherein R1、R2、R3The groups are respectively and independently selected from saturated alkyl, unsaturated alkyl, alkoxy or aryl, and X is halogen.
5. The method of claim 1 or 4, wherein R in Silyl is1、R2、R3The carbon number of the groups is 1-12 independently.
6. The method according to claim 1, wherein the molar ratio of the metal reducing agent M to the red phosphorus to the halosilane is 3:7:3 to 5.
7. The method of claim 1, wherein in the step (2), the cooling temperature is-78 to-20 ℃, and the time for continuing the reaction is 0.5 to 2 hours.
8. The method according to claim 1, wherein in the step (2), the post-processing is: filtering and collecting filtrate under the protection of inert gas, removing the solvent under reduced pressure, and finally washing by a non-polar solvent to obtain the product.
9. The method according to claim 8, wherein the nonpolar solvent is an alkane and/or a cycloalkane, and the carbon number of the nonpolar solvent is not less than 6.
10. A silicon-based phosphorus cluster compound synthesized according to the method of any one of claims 1 to 9.
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Non-Patent Citations (4)
| Title |
|---|
| FRITZ, G.等: ""Substituted heptaphosphanortricyclenes: derivatives and homologs of P7(SiMe3)3"", 《JOURNAL OF ORGANOMETALLIC CHEMISTRY》 * |
| I.KOVACS等: ""Synthese, Charakterisierung und Struktur von P7(t-Bu3Si)3 (,,Tris( supersilyl) heptaphosphan( 3)")[1]"", 《Z. ANORG. ALLG. CHEM.》 * |
| MARIO CICAC-HUDI等: ""Direct Access to Inversely Polarized Phosphaalkenes from Elemental Phosphorus or Polyphosphides"", 《EUROPEAN JOURNAL OF INORGANIC CHEMISTRY》 * |
| SCHMIDBAUR, HUBERT等: ""An improved preparation of tris(trimethylsilyl)heptaphosphine"", 《PHOSPHORUS, SULFUR AND SILICON AND THE RELATED ELEMENTS》 * |
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