CN113912635A - Method for preparing homoallylic silicon derivative by iron catalysis - Google Patents
Method for preparing homoallylic silicon derivative by iron catalysis Download PDFInfo
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- CN113912635A CN113912635A CN202010657055.5A CN202010657055A CN113912635A CN 113912635 A CN113912635 A CN 113912635A CN 202010657055 A CN202010657055 A CN 202010657055A CN 113912635 A CN113912635 A CN 113912635A
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- 238000000034 method Methods 0.000 title claims abstract description 23
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000077 silane Inorganic materials 0.000 claims abstract description 23
- -1 allyl silicon compounds Chemical class 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract 2
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960002089 ferrous chloride Drugs 0.000 claims description 6
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 150000002466 imines Chemical class 0.000 claims description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 5
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims description 3
- 150000003377 silicon compounds Chemical class 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 3
- LFMMVPZBLJZNGE-UHFFFAOYSA-N 2,6-di(propan-2-yl)pyridine Chemical compound CC(C)C1=CC=CC(C(C)C)=N1 LFMMVPZBLJZNGE-UHFFFAOYSA-N 0.000 claims description 2
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- HEJPGFRXUXOTGM-UHFFFAOYSA-K iron(3+);triiodide Chemical compound [Fe+3].[I-].[I-].[I-] HEJPGFRXUXOTGM-UHFFFAOYSA-K 0.000 claims description 2
- FRIJBUGBVQZNTB-UHFFFAOYSA-M magnesium;ethane;bromide Chemical compound [Mg+2].[Br-].[CH2-]C FRIJBUGBVQZNTB-UHFFFAOYSA-M 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims 6
- 125000003118 aryl group Chemical group 0.000 claims 6
- 125000001424 substituent group Chemical group 0.000 claims 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 2
- 229910052794 bromium Inorganic materials 0.000 claims 2
- 239000000460 chlorine Substances 0.000 claims 2
- 229910052801 chlorine Inorganic materials 0.000 claims 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 2
- XMSZANIMCDLNKA-UHFFFAOYSA-N methyl hypofluorite Chemical compound COF XMSZANIMCDLNKA-UHFFFAOYSA-N 0.000 claims 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims 2
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims 1
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims 1
- RJVSRDYLTRTKNC-UHFFFAOYSA-N CNCCNC.[N].[N] Chemical compound CNCCNC.[N].[N] RJVSRDYLTRTKNC-UHFFFAOYSA-N 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- 150000003505 terpenes Chemical class 0.000 abstract description 5
- 235000007586 terpenes Nutrition 0.000 abstract description 4
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 3
- 238000005580 one pot reaction Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 40
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 239000012230 colorless oil Substances 0.000 description 10
- 238000001514 detection method Methods 0.000 description 10
- 235000019439 ethyl acetate Nutrition 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 9
- 238000004896 high resolution mass spectrometry Methods 0.000 description 7
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 230000005311 nuclear magnetism Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 150000003376 silicon Chemical class 0.000 description 2
- 229920005573 silicon-containing polymer Polymers 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XNDNTUOEUNAQAX-UHFFFAOYSA-N 6-propan-2-yl-1h-pyridin-2-one Chemical compound CC(C)C1=CC=CC(=O)N1 XNDNTUOEUNAQAX-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229910019443 NaSi Inorganic materials 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000011954 Ziegler–Natta catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 230000009466 transformation Effects 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- 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
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- 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
- C07F7/0827—Syntheses with formation of a Si-C bond
- C07F7/0829—Hydrosilylation reactions
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- 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
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/04—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
- C08F130/08—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
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- Chemical Kinetics & Catalysis (AREA)
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- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
The invention relates to a method for preparing a homoallylic silicon derivative by iron catalysis. In particular to a one-pot method for preparing terpene and silane under the condition of iron catalysis. The invention starts from simple and easily obtained raw materials and catalysts and obtains a series of high allyl silicon compounds through hydrosilylation reaction.
Description
Technical Field
The invention relates to a method for synthesizing a homoallylic silicon derivative compound.
Background
The organic silicon compound has the unique structure, combines the performances of inorganic materials and organic materials, has the basic properties of low surface tension, small viscosity-temperature coefficient, high compressibility, high gas permeability and the like, has the excellent characteristics of high and low temperature resistance, electrical insulation, oxidation resistance stability, weather resistance, flame retardancy, hydrophobicity, corrosion resistance, no toxicity, no odor, physiological inertia and the like, is widely applied to the industries of aerospace, electronics and electricity, building, transportation, chemical industry, textile, food, light industry, medical treatment and the like, and is mainly applied to sealing, adhesion, lubrication, coating, surface activity, demolding, defoaming, foam inhibition, water prevention, moisture prevention, inert filling and the like. With the continuous increase of the quantity and varieties of organic silicon, the application field is continuously widened, a unique important product system in the new chemical material field is formed, and a plurality of varieties are indispensable and cannot be replaced by other chemicals, so that the organic silicon material has great development potential.
Compared with the traditional synthetic method of high allyl silicon, the invention directly constructs the high allyl silicon compound through the high regioselectivity biomass terpenoid hydrosilation reaction.
In summary, a process for the preparation of high allylic silicon derivatives by hydrosilation of high regioselective terpenoid olefins is described.
Disclosure of Invention
The invention aims to provide a method for synthesizing a high allyl silicon derivative by iron catalysis.
Reaction equation 1: synthesis of homoallylic silicon derivatives
The specific operation steps are as follows (reaction equation 1):
reacting in a reactor, firstly adding a catalyst, a ligand and a solvent, stirring for 1 minute, then adding a reducing agent, silane 1 and olefin 2, and reacting at 40-100 ℃ for 2.0-18.0 hours; after the reaction is finished, the homoallylic silicon derivative 3 is obtained by separation.
The molar ratio of silane 1 to olefin 2 is from 1:1 to 3, preferably 1: 1.5.
The catalyst is one or more than two of ferric chloride, ferric bromide, ferric iodide, ferric acetylacetonate and ferrous chloride, preferably ferrous chloride; the amount of catalyst used is from 1 mol% to 10 mol%, preferably 5 mol%, based on the amount of silane 1 used.
The ligand is one or more than two of phenanthroline, 2-bipyridine, 2, 6-diisopropylpyridine dione imine, mesitylidine dione imine, 2, 6-diisopropylpyridine dialdehyde imine and mesitylidine dialdehyde imine; the amount of ligand used is from 1 mol% to 10 mol%, preferably 5 mol%, of the amount of silane 1 used.
The reducing agent is one or more than two of zinc powder, magnesium powder, manganese powder, sodium triethylborohydride, diethyl zinc and ethyl magnesium bromide, and preferably sodium triethylborohydride; the reducing agent is used in an amount of 1 mol% to 50 mol%, preferably 10 mol%, based on the amount of silane 1.
The solvent is one or more of 1, 4-dioxane, dichloromethane, chlorobenzene, trifluorotoluene, n-hexane and tetrahydrofuran, preferably tetrahydrofuran; the amount of solvent used is 0.1 to 5.0ml, preferably 1.0ml, per mmol of silane 1.
The invention has the following advantages:
first, the reaction is highly regioselective and reacts with terpene substrates to give specific 3, 4-addition homoallylic silicon compounds. Facilitating the further transformation of the derivative material product. Secondly, the terpene substrates needed by the reaction are simple and easily obtained, belong to bulk chemicals and are low in price. Finally, the catalyst used in the reaction system is a simple iron catalyst, and compared with the reported cobalt catalyst, the iron catalyst is low in price and good in biocompatibility.
Detailed Description
For a better understanding of the present invention, the following examples are set forth. The reaction materials and results of examples 1-10 are shown in Table 1.
TABLE 1 reaction results for different substituted silanes, terpenes
Ph is phenyl; TBSO is tert-butyldimethylsilyloxy
Example 1
Reacting in a reactor, firstly adding 0.02mmoL (the dosage is 10mol percent of 1 amount of silane) of ferrous chloride serving as a catalyst, 0.02mmoL (the dosage is 10mol percent of 1 amount of silane) of 2, 6-isopropyl pyridone diimine and tetrahydrofuran (1.0mL) serving as a solvent, stirring for 1 minute, then adding 0.04mmoL (the dosage is 20mol percent of 1 amount of silane) of zinc powder serving as a reducing agent, 1a (0.2mmoL) of silane and 2a (0.3mmoL) of olefin, and reacting at 40 ℃ for 2.0 hours; after the reaction is finished, the yield of the allyl silicon compound 3a is 81% by column chromatography separation, and the structure of the compound is identified by infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum) and high-resolution mass spectrum.
The detection data are as follows:
Colorless oil,46.4mg,92％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.57–7.54(m,4H),7.41–7.30(m,6H),4.87(t,J＝3.7Hz,1H),4.72(s,1H),4.69(s,1H),2.21–2.02(m,2H),1.71(s,3H),1.32–1.26(m,2H).13C NMR(100MHz,CDCl3)δ147.65,135.18,134.31,129.63,128.04,108.99,32.30,22.31,10.38.HRMS calculated for C17H21Si[M+H]+253.1413,found 253.1408.
example 2:
the procedure and conditions were the same as in example 1, except that in example 1, the catalyst was ferric bromide, the amount added was 20% (amount used was 20 mol% based on the amount of silane 1), the yield of product 3b was 94%, and the structure of the compound was identified by infrared, nuclear magnetic (hydrogen and carbon spectroscopy) and high-resolution mass spectrometry, except for the differences shown in table 1.
The detection data are as follows:
3b:Colorless oil,50.0mg,94％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.59–7.51(m,2H),7.46(dd,J＝7.7,1.4Hz,2H),7.40–7.28(m,3H),7.18(d,J＝7.3Hz,2H),4.85(t,J＝3.7Hz,1H),4.72(s,1H),4.68(s,1H),2.34(s,3H),2.12(t,J＝8.4Hz,2H),1.71(s,3H),1.42–1.17(m,2H).13C NMR(100MHz,CDCl3)δ147.74,139.60,135.26,135.18,134.63,130.56,129.56,128.93,128.03,108.96,32.35,22.34,21.60,10.52.HRMS calculated for C18H23Si[M+H]+267.1569,found 267.1562.
example 3:
the operation process and conditions were the same as those in example 1, except that the solvent was chlorobenzene, the yield of the product 3c was 77%, and the structure of the compound was identified by infrared, nuclear magnetic (hydrogen and carbon) spectroscopy, high resolution mass spectrometry, except for the differences shown in table 1.
The detection data are as follows:
3c:Colorless oil,47.2mg,77％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.61–7.54(m,2H),7.51–7.49(m,2H),7.40–7.32(m,5H),4.86(t,J＝3.6Hz,1H),4.72(s,1H),4.69(s,1H),2.19–2.04(m,2H),1.72(s,3H),1.31(s,9H),1.30–1.25(m,2H).13C NMR(100MHz,CDCl3)δ152.62,147.77,135.20,135.06,134.58,130.67,129.54,128.00,125.04,108.91,34.76,32.36,31.27,22.34,10.49.HRMS calculated for C21H28NaSi[M+Na]+331.1858,found 331.1838.
example 4:
the operation process and conditions were the same as those in example 1, except that the reaction temperature was 50 ℃ and the yield of the product 3d was 84%, except for the differences shown in table 1, and the structure of the compound was identified by infrared, nuclear magnetic (hydrogen and carbon spectra) and high resolution mass spectrometry.
The detection data are as follows:
3d:Colorless oil,47.6mg,84％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.51–7.43(m,2H),7.40(d,J＝8.2Hz,2H),7.34–7.21(m,3H),6.84(d,J＝8.1Hz,2H),4.77(t,J＝3.7Hz,1H),4.64(s,1H),4.61(s,1H),3.72(s,3H),2.09–1.99(m,2H),1.63(s,3H),1.22–1.14(m,2H).13C NMR(100MHz,CDCl3)δ160.92,147.75,136.67,135.12,134.78,129.52,128.00,124.90,113.88,108.92,55.05,32.32,22.31,10.61.HRMS calculated for C18H23OSi[M+H]+283.1518,found 283.1509.
example 5:
the procedure and conditions were the same as in example 1, except that, in addition to the differences shown in table 1, the reducing agent was diethylzinc, the amount of addition was 20% (amount of silane 1: 20 mol%), the yield of product 3e was 85%, and the compound was subjected to infrared, nuclear magnetic (hydrogen and carbon spectroscopy) and high-resolution mass spectrometry to identify the structure.
The detection data are as follows:
3e:Colorless oil,55.9mg,85％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.64–7.57(m,8H),7.43–7.32(m,6H),4.92(t,J＝3.7Hz,1H),4.74(s,1H),4.70(s,1H),2.28–2.06(m,2H),1.72(s,3H),1.37–1.28(m,2H).13C NMR(100MHz,CDCl3)δ147.65,142.37,140.95,135.66,135.20,134.26,133.01,129.68,128.83,128.09,127.53,127.19,126.77,109.02,32.32,22.33,10.42.HRMS calculated for C23H25Si[M+H]+329.1726,found 329.1717.
example 6:
the operation procedure and conditions were the same as in example 1, except that the differences shown in table 1 were that the amount of the ferrous chloride catalyst was 5% (the amount was 5 mol% based on the amount of silane 1), the yield of the product 3f was 93%, and the structure of the compound was identified by infrared, nuclear magnetic (hydrogen and carbon) spectroscopy and high-resolution mass spectrometry.
The detection data are as follows:
3f:Colorless oil,49.3mg,93％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.59–7.52(m,2H),7.39–7.30(m,5H),7.25(t,J＝7.4Hz,1H),7.20(d,J＝7.2Hz,1H),4.85(t,J＝3.7Hz,1H),4.72(s,1H),4.69(s,1H),2.33(s,3H),2.22–2.06(m,2H),1.72(s,3H),1.31–1.22(m,2H).13C NMR(100MHz,CDCl3)δ147.73,137.43,135.82,135.20,134.49,134.12,132.22,130.48,129.59,128.04,127.99,108.97,32.35,22.34,21.56,10.44.HRMS calculated for C18H23Si[M+H]+267.1569,found 267.1569.
example 7:
the operation process and conditions are the same as those of example 1, except that the differences shown in Table 1 are that the ligand is 2, 6-diisopropylpyridinedione imine, the addition amount is 10% (the amount is 10 mol% of the amount of silane 1), the yield of 3g of the product is 63%, and the compound is subjected to infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum) and high-resolution mass spectrum to identify the structure.
The detection data are as follows:
3g:Colorless oil,30.8mg,63％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.57–7.48(m,2H),7.41–7.31(m,3H),4.70(s,1H),4.67(s,1H),4.27(p,J＝3.5Hz,1H),2.11–2.01(m,2H),1.71(s,3H),1.53–1.45(m,1H),1.30–1.23(m,2H),1.03–0.96(m,2H),0.91–0.80(m,8H).13C NMR(100MHz,CDCl3)δ147.94,134.66,129.22,127.86,108.76,33.48,32.43,30.80,22.24,22.13,22.11,10.08,9.30.HRMS calculated for C16H27Si[M+H]+247.1882,found 247.1874.
example 8:
the operation process and conditions are the same as those of example 1, and are different from example 1 in that except for the differences shown in table 1, the reducing agent is magnesium powder, the addition amount is 1.0eq. (the amount is 1 amount of silane), the 3h yield of the product is 78%, and the compound is subjected to infrared, nuclear magnetism (hydrogen spectrum and carbon spectrum) and high-resolution mass spectrum to identify the structure.
The detection data are as follows:
3h:Colorless oil,40.3mg,78％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.63–7.45(m,2H),7.40–7.28(m,3H),4.69(s,1H),4.67(s,1H),4.11(q,J＝3.4Hz,1H),2.07–2.02(m,2H),1.81–1.74(m,1H),1.75–1.62(m,7H),1.28–1.11(m,5H),1.09–0.95(m,3H).13C NMR(100MHz,CDCl3)δ148.03,135.09,134.76,129.18,127.78,108.67,32.63,28.36,28.33,27.90,27.88,26.80,23.59,22.27,8.22.HRMS calculated for C17H27Si[M+H]+229.1882,found 259.1880.
example 9:
the operation procedure and conditions were the same as in example 1, except that the reaction time was 18 hours and the yield of the product 3i was 94% except for the differences shown in Table 1, and the compound was subjected to infrared, nuclear magnetic (hydrogen and carbon spectra) and high resolution mass spectrometry, which were different from example 1.
The detection data are as follows:
3i:Colorless oil,60.1mg,94％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.64–7.60(m,4H),7.45–7.38(m,6H),5.15(t,J＝6.0Hz,1H),4.94(t,J＝3.7Hz,1H),4.84(s,1H),4.78(s,1H),2.25–2.18(m,2H),2.16–2.08(m,4H),1.73(s,3H),1.63(s,3H),1.38–1.33(m,2H).13C NMR(100MHz,CDCl3)δ151.34,135.11,134.26,131.50,129.55,127.98,124.15,108.08,35.81,30.68,26.43,25.67,17.66,10.40.HRMS calculated for C22H29Si[M+H]+321.2039,found 321.2041.
example 10:
the operation procedure and conditions were the same as those in example 1, except that the reaction temperature was 80 ℃ and the yield of the product 3j was 77% except for the differences shown in table 1, and the structure of the compound was identified by nuclear magnetic (hydrogen and carbon) spectroscopy and high-resolution mass spectrometry.
The detection data are as follows:
3j:Colorless oil,69.8mg,77％yield,Rf＝0.8(PE/EtOAc 100/1).1H NMR(400MHz,CDCl3)δ7.66–7.54(m,4H),7.49–7.34(m,6H),4.93(t,J＝3.7Hz,1H),4.72(s,1H),4.66(s,1H),2.19(t,8.3Hz,2H),2.05(t,J＝7.4Hz,2H),1.55–1.46(m,2H),1.46–1.38(m,2H),1.38–1.30(m,2H),1.21(s,6H),0.89(s,9H),0.10(s,6H).13C NMR(100MHz,CDCl3)δ151.60,135.12,134.30,129.55,127.98,108.02,73.39,44.72,36.29,30.51,29.81,25.86,22.42,18.10,10.38,-2.04.HRMS calculated for C28H45OSi[M+H]+453.3009,found 453.3005.
application example 1:
reaction equation 2: silicone Polymer Synthesis
The product 3a can be simply converted into an aeronautical sealing silicone polymer material through further polymerization. The specific operation is as follows (formula 2):
under the protection of nitrogen, 3a (0.2mmol) is dissolved in toluene (5.0mL), Ziegler-Natta catalyst (1 mmol% of 3 a) is added, and then the mixture is stirred at 100 ℃ for 24h and quenched at normal temperature by adding 10% by mass hydrochloric acid. After that, extraction was performed with ether, dried over anhydrous sodium sulfate, and rotary-evaporated to give a colorless oily liquid. The compound is subjected to nuclear magnetism (hydrogen spectrum), and the molecular weight range is 3000-5000.
Claims (7)
1. A method for preparing a homoallylic silicon compound by iron catalysis is characterized in that:
conjugated diene 2 and silane 1 shown in the following formula are used as raw materials to generate a homoallylic silicon derivative 3, and the reaction formula is as follows:
wherein R is C1-C20 alkyl, preferably C1-C6 alkyl, more preferably methyl or ethyl;
R1is methyl, ethyl, isopropyl, n-hexyl, cyclohexyl or aryl, wherein the aryl is phenyl or aryl with substituent on benzene ring, the substituent on the benzene ring is 1-2 of methyl, methoxy, fluorine, chlorine and bromine, and the number of the substituent on the benzene ring is 1-2;
R2selecting methyl, ethyl, isopropyl, n-hexyl, cyclohexyl or aryl, wherein the aryl is phenyl or aryl with substituent on benzene ring, the substituent on the benzene ring is 1-2 of methyl, methoxy, fluorine, chlorine and bromine, and the number of the substituent on the benzene ring is 1-2;
the catalyst is an iron catalyst;
the ligand is one or more than two of phenanthroline, 2-bipyridine, 2, 6-diisopropylpyridine dione imine, mesitylidine dione imine, 2, 6-diisopropylpyridine dialdehyde imine and mesitylidine dialdehyde imine.
2. The method of claim 1, wherein:
the specific operation steps are as follows:
reacting in a reactor, firstly adding a catalyst, a ligand and a solvent, stirring and mixing, then adding a reducing agent, silane 1 and olefin 2, and reacting at 20-100 ℃ (preferably 30-60 ℃, more preferably 40 ℃); the reaction time is 0.5 to 24 hours (preferably 1 to 3 hours, more preferably 2.0 hours); after the reaction, allylsilicon derivative 3 was isolated.
3. A method according to claim 1 or 2, characterized in that:
the molar ratio of silane 1 to olefin 2 is from 1:1 to 3, preferably from 1:1.0 to 2.0, more preferably 1: 1.5.
4. A method according to claim 1 or 2, characterized in that:
the catalyst is one or more than two of ferric chloride, ferric bromide, ferric iodide, ferric acetylacetonate and ferrous chloride, preferably ferrous chloride; the amount of catalyst used is from 1 mol% to 10 mol%, preferably from 4 mol% to 6 mol%, more preferably 5 mol% of the amount of silane 1 used.
5. A method according to claim 1 or 2, characterized in that:
the amount of ligand is 1 mol% to 10 mol%, preferably 4 mol% to 6 mol%, more preferably 5 mol% of the amount of silane 1.
6. A method according to claim 1 or 2, characterized in that:
the reducing agent is one or more than two of zinc powder, magnesium powder, manganese powder, sodium triethylborohydride, diethyl zinc and ethyl magnesium bromide, and preferably sodium triethylborohydride; the reducing agent is used in an amount of 1 mol% to 50 mol%, preferably 8 mol% to 15 mol%, more preferably 10 mol% of the amount of silane 1.
7. A method according to claim 1 or 2, characterized in that:
the solvent is one or more of 1, 2-dichloroethane, dichloromethane, chloroform, acetone, nitrogen-nitrogen dimethyl ethylenediamine, acetonitrile, dimethyl sulfoxide, chlorobenzene, trifluorotoluene, 1, 2-dichlorobenzene, tetrahydrofuran and water, preferably 1, 2-dichlorobenzene; the amount of solvent used is 0.1 to 5.0ml, preferably 0.8 to 1.5 ml, more preferably 1.0ml, per mmol of silane 1.
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