CN110627826B - Four-electron homogeneous phase reducing agent, preparation method and application thereof - Google Patents
Four-electron homogeneous phase reducing agent, preparation method and application thereof Download PDFInfo
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- CN110627826B CN110627826B CN201810653138.XA CN201810653138A CN110627826B CN 110627826 B CN110627826 B CN 110627826B CN 201810653138 A CN201810653138 A CN 201810653138A CN 110627826 B CN110627826 B CN 110627826B
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 claims abstract description 43
- -1 ion compound Chemical class 0.000 claims abstract description 32
- 125000003003 spiro group Chemical group 0.000 claims abstract description 29
- 230000009467 reduction Effects 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 23
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 150000001340 alkali metals Chemical class 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 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 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 7
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 abstract description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 2
- 230000003000 nontoxic effect Effects 0.000 abstract description 2
- 230000009967 tasteless effect Effects 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 22
- 238000006722 reduction reaction Methods 0.000 description 20
- 239000000047 product Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 150000003967 siloles Chemical class 0.000 description 6
- 235000018185 Betula X alpestris Nutrition 0.000 description 5
- 235000018212 Betula X uliginosa Nutrition 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- PDZGAEAUKGKKDE-UHFFFAOYSA-N lithium;naphthalene Chemical compound [Li].C1=CC=CC2=CC=CC=C21 PDZGAEAUKGKKDE-UHFFFAOYSA-N 0.000 description 4
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- FXORZKOZOQWVMQ-UHFFFAOYSA-L dichloropalladium;triphenylphosphane Chemical compound Cl[Pd]Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 FXORZKOZOQWVMQ-UHFFFAOYSA-L 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- UKOVZLWSUZKTRL-UHFFFAOYSA-N naphthalid Chemical compound C1=CC(C(=O)OC2)=C3C2=CC=CC3=C1 UKOVZLWSUZKTRL-UHFFFAOYSA-N 0.000 description 3
- 239000012454 non-polar solvent Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- ROWKJAVDOGWPAT-UHFFFAOYSA-N Acetoin Chemical compound CC(O)C(C)=O ROWKJAVDOGWPAT-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N Glycolaldehyde Chemical compound OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 description 2
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 description 2
- 238000001941 electron spectroscopy Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005272 metallurgy Methods 0.000 description 2
- 230000005311 nuclear magnetism Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UAWABSHMGXMCRK-UHFFFAOYSA-L samarium(ii) iodide Chemical compound I[Sm]I UAWABSHMGXMCRK-UHFFFAOYSA-L 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- YTBSYETUWUMLBZ-UHFFFAOYSA-N D-Erythrose Natural products OCC(O)C(O)C=O YTBSYETUWUMLBZ-UHFFFAOYSA-N 0.000 description 1
- YTBSYETUWUMLBZ-IUYQGCFVSA-N D-erythrose Chemical compound OC[C@@H](O)[C@@H](O)C=O YTBSYETUWUMLBZ-IUYQGCFVSA-N 0.000 description 1
- MNQZXJOMYWMBOU-VKHMYHEASA-N D-glyceraldehyde Chemical compound OC[C@@H](O)C=O MNQZXJOMYWMBOU-VKHMYHEASA-N 0.000 description 1
- ZAQJHHRNXZUBTE-WUJLRWPWSA-N D-xylulose Chemical compound OC[C@@H](O)[C@H](O)C(=O)CO ZAQJHHRNXZUBTE-WUJLRWPWSA-N 0.000 description 1
- 206010056474 Erythrosis Diseases 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
- ZDPOWKYUIAUPLP-UHFFFAOYSA-L dilithium;diphenoxide Chemical compound [Li+].[Li+].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 ZDPOWKYUIAUPLP-UHFFFAOYSA-L 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UQPHVQVXLPRNCX-UHFFFAOYSA-N erythrulose Chemical compound OCC(O)C(=O)CO UQPHVQVXLPRNCX-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 150000002681 magnesium compounds Chemical class 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000082 organogermanium group Chemical group 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229940002612 prodrug Drugs 0.000 description 1
- 239000000651 prodrug Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0805—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms
- C07F7/0807—Compounds with Si-C or Si-Si linkages comprising only Si, C or H atoms comprising Si as a ring atom
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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Abstract
The invention discloses a 2,3,4,5,2',3',4',5' -octa-aryl spiro silole tetranegative ion compound with a structure of formula (I),
in the formula, ar is C 6 ～C 10 An aromatic group or substituted aromatic group, preferably one of phenyl, 2,6-dimethylphenyl, or 2,6-diisopropylphenyl. The reducing agent is used for diquinone, bis (triphenylphosphine) palladium dichloride, methyl iodide and oxygen systems to show high-efficiency reduction performance, and the thermal stability, the solubility and the chemical stability of the reducing agent are good; the preparation method is simple and the yield is high; the aryl spiro silole compound is safe to use, nontoxic, tasteless and environment-friendly, and has a wider application prospect in homogeneous reducing agents. The invention further discloses a preparation method and application of the aryl spiro silole tetraanion compound.
Description
Technical Field
The invention relates to a homogeneous phase reducing agent, a preparation method and application thereof, in particular to a four-electron homogeneous phase reducing agent containing a spiro silole structure, a preparation method and application thereof.
Background
The reduction reaction is an important reaction in the field of synthetic chemistry, and is widely applied to metallurgy, chemical engineering, materials and biomedicine. The reducing agents commonly used today are mainly some alkali metals and alkaline earth metals, such as: metallic lithium (Li), sodium (Na), potassium (K), magnesium (Mg), and the like. However, the reducing agents of the above types are heterogeneous reducing agents, and they are immiscible with the reaction system, so that the reaction is slow to proceed, the reaction selectivity is poor, and excessive reduction is easily caused. The homogeneous phase reducing agent can avoid the problems, the homogeneous phase reducing agent and a reduction system can be mutually dissolved and quantitatively react, the reaction is easy to control, the obtained reduction product is single, and the yield is high.
At present, the common homogeneous reducing agents mainly comprise lithium naphthalene, birch reagent and samarium diiodide (SmI) 2 ) And so on. Birch reported in 1944 that a homogeneous system single-electron reducing agent of metal lithium and sodium dissolved in a liquid ammonia solvent can efficiently reduce aldehyde and ketone, and is named as a Birch reducing agent (see Birch, a, j.j.chem.soc. 1944.430) and has wide application in synthetic chemistry (see Birch, a, j.j.chem.soc.1946.593; j.chem.soc. 1947.102). Samaric diiodide homogeneous one-electron reductants were reported in 1980 by h.b.kagan (see Girard, p.; namy, j.l.; kagan, h.b.j.am. Chem. Soc.1980,102, 2693), which were named as Kagan reagents, can achieve highly efficient asymmetric reduction of imines, aldehydes, ketones, etc., into the most commonly used homogeneous one-electron reductants at present (see Krief, a.; laval, a.m.chem.rev. 1999,99,745). Lithium naphthanate is also a commonly used homogeneous reducing agent, particularly in inorganic synthesis, elemental organic chemistry and anionThe field of subpolymerization, has found a very wide range of applications (see Molander, G.A. chem. Rev.1992,92,29).
Compared with a single-electron homogeneous phase reducing agent, the multi-electron reducing agent can release a plurality of electrons simultaneously in the reduction reaction, can accelerate the reduction reaction and improve the selectivity of the reduction reaction, and particularly shows obvious advantages in the fields of element organic synthesis chemistry, metallurgy and pharmacy.
Chinese patent CN103274950A reports a homogeneous phase two-electron reducing agent ammonium thiosulfate which can efficiently reduce nitrobenzene to prepare aniline. Specifically, nitrobenzene takes ammonium thiosulfate as a reducing agent in an alcoholic solution, and carries out reduction reaction at 30-100 ℃, and aniline is obtained after complete reaction and post-treatment.
US5,831,097, EP0364752, US4,950,306 all disclose that certain alpha-hydroxycarbonyl compounds are effective reducing agents in the dye industry, provided that a sufficient amount of base needs to be added to the reaction medium.
Chinese patent CN103315995a unexpectedly found that certain α -hydroxycarbonyl compounds have effective reducing power at low pH values and can therefore be used in mild environments (and/or in the presence of large amounts of non-aqueous (organic) solvents) to reduce a variety of structures, including a variety of organic compounds. The patent reports that alpha-hydroxy carbonyl compounds capable of forming cyclic dimers can be used as homogeneous two-electron reducing agents to reduce and activate some prodrugs, and are widely applied to the field of drug research and development. Examples of alpha-hydroxycarbonyl compounds used are dihydroxyacetone, glycolaldehyde, glyceraldehyde, erythrose, xylulose, erythrulose, or 3-hydroxy-2-butanone.
In 2007, cameron Jones reported in the journal of Science the first monovalent magnesium compound in the world (formula a), which was demonstrated by various chemical reactions to undergo a two-electron transfer reaction, to be converted to divalent magnesium in the presence of an oxidizing agent (see Science 2007,318,1754), and which, upon reduction of some substrates, such as organogermanium and aluminum compounds, showed superior performance in terms of selectivity to traditional heterogeneous and homogeneous one-electron reducing agents (see angels.chem.int.ed.2009, 48,9701 nat.chem. 2010,2,865..
Silole compounds (silacyclopentadiene compounds) are widely applied to the fields of optical instruments, chemical sensing, biological monitoring, cell imaging and stimulation nano response materials due to unique chemical and photoelectric properties, particularly, electrons can be easily obtained by the silole compounds due to the low LUMO orbital energy of the silole compounds, the silole compounds can be reduced by alkali metals to generate silole negative ion compounds, and the silole negative ion compounds are very active at room temperature and can easily react to generate silole polymers, so that the research on the chemical properties and the purposes of the silole compounds is limited.
Disclosure of Invention
The inventor finds that the four-electron homogeneous phase reducing agent with the spiro silole structure and high efficient reduction performance can be separated by adopting substituent with strong conjugation ability to delocalize negative ions on the silole ring and stabilizing the silole negative ion compound by using a specific oxygen-containing coordination solvent.
It is therefore an object of the present invention to provide a four-electron homogeneous reductant compound, to disclose a process for its preparation, and to disclose its use.
The four-electron homogeneous phase reducing agent is 2,3,4,5,2',3',4',5' -octaaryl spiro silole tetra-negative ion compound, and the structure is shown as the formula (I):
in the formula, ar is C 6 ～C 10 An aromatic group or a substituted aromatic group.
Ar is preferably one of phenyl, 2,6-dimethylphenyl or 2,6-diisopropylphenyl.
And M is an alkali metal.
The M is selected from one of metallic lithium, sodium or potassium, and is preferably metallic lithium.
The S is an oxygen-containing solvent and is complexed with the silole compound in a coordination bond form.
S is selected from one of tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether, and ethylene glycol dimethyl ether is more preferable.
The invention also discloses a preparation method of at least one four-electron homogeneous phase reducing agent with the structure shown in the formula (I).
The preparation method of the four-electron homogeneous phase reducing agent is characterized in that an aryl spiro silole compound with a structure shown in a formula (II) is used as a raw material, the aryl spiro silole compound is obtained by reducing an alkali metal in an oxygen-containing solvent at the temperature of-20 ℃, the molar mass ratio of the aryl spiro silole compound to the alkali metal to the oxygen-containing solvent is 1 (2-4) to (8-10), and the reaction time is 0.5-2 h.
Wherein Ar of the starting compound of formula (II) is C 6 ～C 10 An aromatic group or substituted aromatic group, preferably one of phenyl, 2,6-dimethylphenyl, or 2,6-diisopropylphenyl.
The preparation of aryl spirocyclic silole starting compounds of formula (II) is described in the literature (Junghyun, lee.; suning Wang.2,5-Functionalized Spiro-Biloles as highlyeffective ingredients Yellow-Light Emitters in electrolytic devices Adv. Funct. Mater.2006,16,681.).
The oxygen-containing organic solvent is one of tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether, and ethylene glycol dimethyl ether is preferred.
The alkali metal is one of lithium, sodium or potassium, and is preferably metallic lithium.
The aryl spiro silole tetraelectron homogeneous phase reducing agent obtained by the invention can be applied to some standard homogeneous phase reduction systems.
In order to illustrate the reduction performance of the invention, the inventor takes a spiro silole tetralithium salt as an example, and respectively reacts with diquinone, bis triphenylphosphine palladium dichloride, methyl iodide and oxygen, and proves that the spiro silole tetralithium salt can completely reduce the oxidant through nuclear magnetic resonance and X-ray energy spectrum characterization technologies.
The preparation and reduction processes of the aryl spiro silole compound are shown as the following formula, wherein 2 represents octaaryl spiro silole tetraanion, and 1 represents octaaryl spiro silole.
In the reaction, the octaaryl spiro silole tetraanions can completely reduce the above substrates of diquinone, bis triphenylphosphine palladium dichloride, methyl iodide and oxygen into lithium diphenolate, zero-valent palladium, methyl lithium and lithium oxide, and the octaaryl spiro silole tetraanions are oxidized into the octaaryl spiro silole and show efficient reduction performance.
The four-electron homogeneous phase reducing agent of the formula (I) has the following characteristics and advantages:
(1) Has good thermal stability, and can not be decomposed even at the temperature of more than 200 ℃.
(2) Has good dissolvability and good dissolvability in a nonpolar solvent n-hexane.
(3) The chemical stability is good, further reaction with the reduction product can be avoided, and the reduction product can be conveniently recycled and reused by a chromatographic column and a recrystallization method.
(4) The preparation method is simple, does not need any catalyst, can carry out the operation within a short time (less than 2 h) and at a mild temperature (20 ℃ below zero), has the yield of over 95 percent and is convenient for large-scale production.
(5) The reducing agent is safe to use, nontoxic, tasteless and environment-friendly.
The advantages endow the aryl spiro silole compound with wider application prospect in homogeneous reducing agents, and have practical significance in silole chemistry and homogeneous reducing agent chemistry.
Drawings
FIG. 1 nuclear magnetic hydrogen spectrum of 2,3,4,5,2',3',4',5' -octaphenyl spiro silole tetralithium salt of product in example 1 ((S)) 1 H NMR C 6 D 6 )。
FIG. 2 Nuclear magnetic silica Spectroscopy (NMR) of 2,3,4,5,2',3',4',5' -octaphenyl Spirocyclic silole tetralithium salt of product from example 1 29 Si NMR C 6 D 6 )。
FIG. 3 nuclear magnetism of hydroquinone as a reduction product in example 2: ( 1 H NMR CDCl 3 ) A hydrogen spectrum.
FIG. 4 example 5X-ray Electron Spectroscopy (XPS) of the reaction product of spirocyclosilole tetralithium salt and bis-triphenylphosphine palladium dichloride.
Detailed Description
The following examples are further illustrative of the technical solutions of the present invention, but the scope of the present invention is not limited by the examples.
1. Principal analytical method
Common solvents such as tetrahydrofuran, normal hexane and anhydrous ether used in experiments are used, and benzophenone is used as an indicator and is refluxed and dewatered by metal sodium under the protection of nitrogen before use; for experiments C 6 D 6 And CDCl 3 Purchased from cambridge isotope laboratories, usa. The chemical raw materials used in the experiment, namely tolane, n-butyllithium, alcohol and silane, are all pure reagent products and are respectively ordered from Aladdin and domestic reagent companies according to requirements. The NMR spectra were obtained at room temperature using a Bruker AV400 NMR spectrometer. The compound is prepared by 1 H NMR， 13 C NMR， 29 Si NMR was carried out to confirm the above results, and comparison of known compounds with the literature was carried out. Of all compounds 1 H NMR、 13 C NMR、 29 The nuclear magnetic data such as Si NMR are measured on a Bruke AV 400M type nuclear magnetic spectrometer, the detection temperature is room temperature (298K) without special description, and the chemical shifts are determined by taking a deuterated solvent as reference: delta 1 H(C 6 D 6 )＝ 7.15ppm，δ 13 C(C 6 D 6 ) =128.00ppm. Samples of compounds that were not sensitive to water oxygen in this experiment were formulated directly in air with untreated deuterated reagents.
2. Raw material source and specification
3. Preparation of 2,3,4,5,2',3',4',5' -octaphenyl spirocyclosilole starting compound
Under the protection of nitrogen, adding metallic lithium (0.28g, 40.0 mmol) into tolane (7.0 g,40.0 mmol) dissolved in 100mL of anhydrous ether at room temperature for 2h, and filtering out the residual metallic lithium; slowly dripping 100mL of toluene solution of silicon tetrachloride (1.7g, 10.0mmol) into the system at-20 deg.C, reacting at room temperature for 1h, slowly heating to room temperature, and continuously heating to 100 deg.C for 2h; then cooling to room temperature, concentrating the solution to 20mL, placing in a refrigerator at-40 ℃ for crystallization to obtain 2,3,4,5,2',3',4',5' -octaphenyl spiro silole 3.3g as a yellow-green solid, wherein the yield is 90% for later use.
Example 1, 3,4,5,2',3',4',5' -Octaphenyl Spirocyclic silole Tetralithium salt preparation
Metallic lithium (0.30g, 44.0mmol) was added to 2,3,4,5,2',3',4',5' -octaphenylspirosilole (7.4 g, 10.0mmol) dissolved in 50mL of ethylene glycol dimethyl ether at room temperature under nitrogen protection. The reaction is carried out for 2 hours, the solution is concentrated to 10mL and is placed in a refrigerator at the temperature of minus 40 ℃ for crystallization, and 11.3g of orange red solid 2,3,4,5,2',3',4',5' -octaphenyl spiro silole tetra lithium salt can be obtained with the yield of 95 percent.
Subjecting the obtained product to nuclear magnetic hydrogen spectrum ( 1 H NMR C 6 D 6 ) As in fig. 1. As can be seen from the figure, δ = 6.87-7.47 ppm is the peak of spiro silole eight phenyl groups, δ =2.98 and δ =3.07ppm are the peak of methylene and methyl groups on ethylene glycol dimethyl ether, and the peak is obviously changed compared with the peak of free ethylene glycol dimethyl ether (δ =3.12 and δ =3.33 ppm). The glycol dimethyl ether is used as a coordination solvent to play a role in stabilizing spiro silole tetralithium salt.
Nuclear magnetic silicon spectrum of the product: ( 29 Si NMR C 6 D 6 ) In FIG. 2, delta = -13.28ppm of typical four-coordinate siliconThe peak range of the silicon spectrum is consistent with that of the target product.
Comparative example 1
Metallic lithium (0.30g, 44.0mmol) was added to 2,3,4,5,2',3',4',5' -octaphenylspirosilole (7.4 g, 10.0mmol) dissolved in 50mL of n-hexane at room temperature under nitrogen protection. Reacting for 2h, concentrating the solution to 10mL, placing the solution in a refrigerator at the temperature of minus 40 ℃ for crystallization, and obtaining the corresponding spirocyclic silole tetralithium salt without separation through nuclear magnetic tracking.
The method is characterized in that the generated spiro silole tetralithium salt is very active in a nonpolar solvent n-hexane, and the nonpolar solvent n-hexane cannot coordinate stable metal lithium ions, so that the final product spiro silole tetralithium salt cannot be separated.
Comparative example 1'
Metallic lithium (0.30g, 44.0mmol) was added to 2,3,4,5,2',3',4',5' -octaphenylspirosilole (7.4g, 10.0mmol) dissolved in 50mL of toluene at room temperature under nitrogen protection. Reacting for 2h, concentrating the solution to 10mL, placing the solution in a refrigerator at the temperature of minus 40 ℃ for crystallization, providing nuclear magnetic detection, and obtaining the corresponding spirocyclic silole tetralithium salt without separation.
It is shown that in toluene, the generated spiro silole tetralithium salt is very active and cannot be effectively separated.
EXAMPLE 2 reaction of spirocyclic Silole Tetralithium salt with diquinone
2,3,4,5,2',3',4',5' -octaphenylspirocyclosilole tetralithium salt is prepared as in example 1.
A solution of diquinone (0.027g, 0.25mmol) in 10mL of tetrahydrofuran was added dropwise to the octaphenylspirocyclosilole tetralithium salt (0.80g, 0.50mmol) obtained in example 1 at room temperature, and the color of the system gradually changed to colorless. The nuclear magnetism of the crude product after being dried by pumping shows that hydroquinone negative ions are generated (the peak is given at the position of sigma =9.83 ppm) and the spirocyclic silole tetralithium salt is completely converted into the spirocyclic silole compound (as shown in figure 3).
The spiro silole tetralithium salt can effectively reduce diquinone by being used as a homogeneous four-electron reducing agent, and shows the property of the homogeneous reducing agent.
Comparative example 2 reaction of lithium metal with diquinone under the same conditions
Adding metallic lithium (0.35g, 0.50mmol) into 10mL of diquinone (0.027g, 0.25mmol) solution dissolved in tetrahydrofuran at room temperature, reacting for 2h, wherein the color of the system is not obviously changed, reacting for 24h, gradually changing to be colorless, and completely reducing the diquinone through nuclear magnetic monitoring.
Compared with common heterogeneous reducing agent metallic lithium, the spiro silole tetralithium salt serving as the homogeneous four-electron reducing agent can efficiently reduce diquinone in a shorter time, and shows the property superior to that of the traditional heterogeneous reducing agent.
Comparative example 2 reaction of lithium naphthalide with diquinone under the same conditions
Lithium naphthalide (0.75g, 0.50mmol) was added to 10mL of diquinone (0.027 g,0.25 mmol) in tetrahydrofuran at room temperature, after 6h reaction, the system gradually turned colorless, and the diquinone was completely reduced by nuclear magnetic monitoring.
Compared with common homogeneous phase one-electron reducing agent naphthalene lithium, the spiro silole tetralithium salt as the homogeneous phase four-electron reducing agent can efficiently reduce diquinone in a shorter time, and shows the property superior to that of the traditional homogeneous phase reducing agent.
EXAMPLE 3 reaction of spirocyclic Silole Tetralithium salt with methyl iodide
2,3,4,5,2',3',4',5' -octaphenylspirocyclosilole tetralithium salt is prepared as in example 1.
A solution of iodomethane (0.07g, 0.5 mmol) dissolved in 5mL of tetrahydrofuran was added dropwise to the spirocyclosilole tetralithium salt obtained in example 1 (0.40g, 0.25mmol, product of example 1) at room temperature, and the color of the system gradually changed to colorless. The drying to obtain a crude product shows that a reduction product methyllithium (MeLi) is generated, and the spiro silole tetralithium salt is completely converted into the spiro silole compound.
The spiro silole tetralithium salt can effectively reduce methyl iodide by being used as a homogeneous four-electron reducing agent, and shows the property of the homogeneous reducing agent.
Comparative example 3 reaction of lithium naphthalene with methyl iodide under the same conditions
Lithium naphthalide (0.75g, 0.50mmol) was added to a solution of 5mL of iodomethane (0.07 g,0.5 mmol) in tetrahydrofuran at room temperature and after 2h reaction the color of the system gradually turned colorless and no separation was observed by nuclear magnetic monitoring to give methyllithium product.
Because lithium naphthalene is a common homogeneous one-electron reducing agent, the selectivity is poor, methyl iodide is easy to be subjected to transition reduction, a plurality of byproducts are generated, the final reduction product is very complex, and a single product cannot be obtained.
EXAMPLE 4 reaction of spirocyclosilole tetralithium salt with oxygen
2,3,4,5,2',3',4',5' -octaphenylspirocyclosilole tetralithium salt is prepared as in example 1.
At room temperature, the spiro silole tetralithium salt (0.40g, 0.25mmol) is exposed in the air for 2h, the system gradually becomes light yellow, and the spiro silole compound is obtained by separation.
The spiro silole tetralithium salt serving as a homogeneous four-electron reducing agent can effectively reduce common oxidant oxygen and shows the property of the homogeneous reducing agent.
EXAMPLE 5 reaction of Spirocyclic Silole Tetralithium salt with bis-triphenylphosphine Palladium dichloride
2,3,4,5,2',3',4',5' -octaphenyl spirocyclosilole tetralithium salt is prepared as in example 1.
Spirocyclothiapyrrole tetralithium salt (0.40g, 0.25mmol) and bis triphenylphosphine palladium dichloride (0.36 g, 0.50mmol) were dissolved in 10mL tetrahydrofuran at room temperature and reacted for 2h, the system was completely pale yellow, and a black precipitate was formed at the bottom of the reaction flask. The black precipitate was characterized by X-ray electron spectroscopy (XPS) as shown in figure 4,
wherein the peak discharge of the X-ray energy spectrum Pdo d (335.1 ev and 340.9 ev) is completely coincident with that of zero-valent palladium. The spiro silole tetralithium salt is used as a four-electron homogeneous phase reducing agent, and can efficiently reduce inorganic metal compounds.
Comparative example 5 reaction of lithium metal with bis-triphenylphosphine palladium dichloride under the same conditions
At room temperature, metal lithium (0.7g, 1.0 mmol) and bis (triphenylphosphine) palladium dichloride (0.36g, 0.50mmol) are dissolved in 10mL of tetrahydrofuran, and the reaction is carried out for 12 hours, so that the system is faded, and divalent palladium is reduced to zero-valent palladium.
Compared with a heterogeneous metal lithium reducing agent, the spiro silole tetralithium salt serving as the homogeneous four-electron reducing agent can effectively reduce a common divalent palladium compound of high-valence metal salt in a shorter time.
The present invention is capable of other embodiments, and various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (7)
1. A four-electron homogeneous phase reducing agent is characterized in that the reducing agent is 2,3,4,5,2',3',4',5' -octaaryl spiro silole tetra-negative ion compound, and the structure is shown as formula (I):
wherein Ar is one of phenyl, 2,6-dimethylphenyl or 2,6-diisopropylphenyl; m is an alkali metal; s is selected from one of tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether and is complexed with the silole compound in the form of a coordination bond.
2. The homogeneous reducing agent according to claim 1, wherein M in formula (I) is selected from one of lithium, sodium or potassium metals.
3. Homogeneous reducing agent according to claim 2, characterized in that M is selected from metallic lithium.
4. The homogeneous reducing agent according to claim 1, wherein S is selected from ethylene glycol dimethyl ether.
5. The preparation method of the homogeneous reducing agent according to claim 1, wherein the preparation method of the reducing agent is to use the aryl spiro silole compound with the structure of formula (II) as a raw material, the compound of formula (II) is obtained by reducing the aryl spiro silole compound with alkali metal in an oxygen-containing solvent at the temperature of-20 ℃ to 20 ℃, the molar mass ratio of the aryl spiro silole compound to the alkali metal to the oxygen-containing solvent is 1 (2-4) to (8-10), the reaction time is 0.5-2 h,
wherein Ar in the raw material compound of the formula (II) is one of phenyl, 2,6-dimethylphenyl or 2,6-diisopropylphenyl; the oxygen-containing organic solvent is one of tetrahydrofuran, diethyl ether or ethylene glycol dimethyl ether.
6. The method of claim 5, wherein the oxygen-containing organic solvent is selected from the group consisting of ethylene glycol dimethyl ether.
7. Use of a four-electron homogeneous reducing agent according to any one of claims 1 to 4, wherein the reducing agent is used in the reduction of diquinone, oxygen, methyl iodide, bis-triphenylphosphine palladium dichloride.
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| Synthesis and NMR characterization of a spirosilole tetra-anion: a homogeneous four-electron reductant;Zhengang Han et al;《MAIN GROUP METAL CHEMISTRY》;20180718;全文 * |
| 噻咯类有机小分子光电材料;毛林燕等;《化学进展》;20091024(第10期);全文 * |
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