CN110229180A - A kind of method that selectivity prepares alkenyl silanes - Google Patents
A kind of method that selectivity prepares alkenyl silanes Download PDFInfo
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- CN110229180A CN110229180A CN201910640507.6A CN201910640507A CN110229180A CN 110229180 A CN110229180 A CN 110229180A CN 201910640507 A CN201910640507 A CN 201910640507A CN 110229180 A CN110229180 A CN 110229180A
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- 238000000034 method Methods 0.000 title claims abstract description 10
- -1 alkenyl silanes Chemical class 0.000 title claims description 11
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000003446 ligand Substances 0.000 claims abstract description 29
- 150000001336 alkenes Chemical group 0.000 claims abstract description 25
- 150000004756 silanes Chemical class 0.000 claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 66
- 238000002360 preparation method Methods 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims 1
- 125000001424 substituent group Chemical group 0.000 claims 1
- 230000033228 biological regulation Effects 0.000 abstract description 4
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 68
- 239000000047 product Substances 0.000 description 23
- QFEOTYVTTQCYAZ-UHFFFAOYSA-N dimanganese decacarbonyl Chemical compound [Mn].[Mn].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] QFEOTYVTTQCYAZ-UHFFFAOYSA-N 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 239000003480 eluent Substances 0.000 description 17
- 238000007789 sealing Methods 0.000 description 17
- 238000003756 stirring Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 229910019443 NaSi Inorganic materials 0.000 description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000002444 silanisation Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
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- 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
-
- 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
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic 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
- 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
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
-
- 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
- C07F7/12—Organo silicon halides
- C07F7/121—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20
- C07F7/122—Preparation or treatment not provided for in C07F7/14, C07F7/16 or C07F7/20 by reactions involving the formation of Si-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
-
- 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
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07J—STEROIDS
- C07J1/00—Normal steroids containing carbon, hydrogen, halogen or oxygen, not substituted in position 17 beta by a carbon atom, e.g. estrane, androstane
- C07J1/0051—Estrane derivatives
- C07J1/0081—Substituted in position 17 alfa and 17 beta
- C07J1/0088—Substituted in position 17 alfa and 17 beta the substituent in position 17 alfa being an unsaturated hydrocarbon group
- C07J1/0092—Alkenyl derivatives
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
It is a kind of to be realized by ligand regulation to the alkylated method of the selective silicon of terminal olefin, it is using terminal olefin and trisubstituted silane as raw material, using benzotrifluoride as solvent, at 140 DEG C, it is reacted under the action of ligand 1 for 24 hours, the dehydrogenation silication product of anti-configuration is obtained with single selective.
Description
Technical field
A kind of method that selectivity prepares alkenyl silanes.
Background technique
Organosilicon is widely used in building, electronics industry, medicine and food etc. as a kind of important industrial chemicals
Field [referring to: (a) Silicon, 2009,1,147. (b) Chem.Rev., 2010,110,1233. (c) Chem.Soc.Rev.,
2011,40,696].Although prepared using transition metal-catalyzed this kind of compound had more report [referring to: (a)
Nat.Rev.Chem., the RSC Adv. of 2018,2,15. (b) Science, 2002,298,204. (c), 2015,5,20603.], but
Be following problem generally existing for the Silanization reaction of alkene: 1. byproduct of reaction is more；2. based on hydrogen silication product,
The product for efficiently synthesizing dehydrogenation silication is rarely reported；3. substrate applicability is poor；4. in dehydrogenation silicification reaction, need additional hydrogen by
Body or oxidant, Atom economy are poor.Meanwhile manganese is used as one kind nontoxic and environmentally friendly metal, the rich content in the earth's crust,
Compared with Fe, other lower valency metals such as Co, Ni show good water oxygen tolerance, the synthesis of the manganese catalysis of recent report
Strategy relates generally to the hydrogen silicification reaction of alkene.Dehydrogenation silication with medium selectivity to some activated olefins and chemical steric hindrance compared with
Big silane is reacted, however has poor compatibility for disactivation alkene and complicated molecule and other kinds of silane
Property [referring to: (a) Chin.J.Chem., 2018,36,1047. (b) Chem.Asian J., 2018,13,2307.].Therefore, it sends out
A kind of effective synthetic method is opened up, highly selective prepares alkenyl silanes and alkyl silane, is always the research emphasis in the field.
In the case where not additional any additive, only by the regulation of ligand, realization includes ethylene, propylene etc. to a plurality of types of alkene
The Silanization reaction of gas, synthetic method are simple and efficient, and have biggish commercial application potentiality.
Summary of the invention
The selective silicon alkylated reaction to alkene is realized the technical problem to be solved by the present invention is to the regulation by ligand
And its application.
Synthetic route of the invention is as follows:
A kind of method that selectivity prepares alkenyl silanes, it is with terminal olefin (1) and trisubstituted silane (2) for original
Material, using benzotrifluoride as solvent, at 115-160 DEG C, is reacted 24-36 hours under the action of ligand 1, is obtained with single selective
To the dehydrogenation silication product (3) of anti-configuration, the ligand 1 is just like flowering structure:
Above-mentioned preparation method, the terminal olefin (1) can be ethylene, propylene and butylene or with various substitutions
The activated olefins or disactivation alkene and some terminal olefins containing labyrinth of base.
The R base of above-mentioned preparation method, the trisubstituted silane (2) can be identical or not identical.
The R base of above-mentioned preparation method, the trisubstituted silane (2) can be ethyl, ethyoxyl, trimethyl silicane oxygen
Base, alkyl or cycloalkyl.
Above-mentioned preparation method, reaction condition are not need extra padding inert gas under air conditions.
The molar ratio of above-mentioned preparation method, the terminal olefin and three substituted silanes is 1:1.
Above-mentioned preparation method, when preparing dehydrogenation silication product, the dosage of catalyst decacarbonyldimanganese is terminal olefin
(1) the 5% of molal quantity, the dosage of ligand 1 are the 10% of terminal olefin (1) molal quantity.
Typical reaction is as follows:
Method of the invention, method are simple and efficient, and selectivity is high, and substrate applicability is strong, and raw material availability is high, especially de-
The initiative single selective realized under ligand regulation in hydrogen silication direction, avoids industrial application in the process due to by-product
The problem of quality decline caused by introducing and separation difficulty.
Specific embodiment
Ligand 1 is synthesized according to document (Adv.Synth.Catal.2015,357,3538).
It will be helpful to understand the present invention using following embodiments, but be not intended to limit the contents of the present invention.
Embodiment 1
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(118mg, 1.00mmol) and HSiEt3
(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room temperature.Instead
Liquid is answered to be concentrated, column chromatographs to obtain product191mg (eluent: petroleum ether, 60-90 DEG C) yield
82%.1H NMR(CDCl3, 500MHz) and δ=7.36 (d, J=8.0Hz, 2H), 7.15 (d, J=8.0Hz, 2H), 6.88 (d, J=
19.2Hz, 1H), 6.37 (d, J=19.2Hz, 1H), 2.35 (s, 3H), 1.00 (t, J=7.9Hz, 9H), 0.67 (q, J=
7.9Hz,6H)；13C NMR(CDCl3, 125MHz) and δ=144.7,137.8,135.9,129.2,126.2,124.5,21.2,
7.4,3.6.
Embodiment 2
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(110mg, 1.00mmol) and HSiEt3
(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room temperature.Instead
Liquid is answered to be concentrated, column chromatographs to obtain product164mg (eluent, with embodiment 1.) yield 73%.1H NMR
(CDCl3, 500MHz) δ=7.20-7.16 (m, 1H), 7.00-6.95 (m, 1H), 6.17 (d, J=19.0Hz, 1H), 0.99 (t,
J=8.0Hz, 9H), 0.65 (q, J=8.0Hz, 6H)；13C NMR(CDCl3, 125MHz) and δ=145.5,137.4,127.4,
125.8,125.4,124.6,7.4,3.5.
Embodiment 3
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(162mg, 1.00mmol) and
HSiEt3(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room
Temperature.Reaction solution concentration, column chromatograph to obtain product233mg (eluent: petroleum ether: acetic acid second
Ester=20:1) yield 84%.1HNMR(CDCl3, 500MHz) and δ=7.45 (d, J=8.6Hz, 2H), 7.06 (d, J=8.6Hz,
2H), 6.87 (d, J=19.2Hz, 1H), 6.38 (d, J=19.2Hz, 1H), 2.30 (s, 3H), 0.98 (t, J=8.0Hz, 9H),
0.66 (q, J=8.0Hz, 6H)；13C NMR(CDCl3, 125MHz) and δ=169.5,150.3,143.7,136.4,127.3,
126.3,121.6,21.2,7.4,3.5.
Embodiment 4
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(138mg, 1.00mmol) and HSiEt3
(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room temperature.Instead
Liquid is answered to be concentrated, column chromatographs to obtain product(eluent is the same as embodiment 1 by 195mg.) yield 77%.1H
NMR(CDCl3, 500MHz) and δ=7.37 (d, J=8.5Hz, 2H), 7.30 (d, J=8.5Hz, 2H), 6.84 (d, J=19.3Hz,
1H), 6.41 (d, J=19.3Hz, 1H), 0.99 (t, J=7.9Hz, 9H), 0.67 (q, J=7.9Hz, 6H)；13C NMR
(CDCl3, 125MHz) and δ=143.4,137.0,133.5,128.6,127.5,126.9,7.4,3.5.
Embodiment 5
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(154mg, 1.00mmol) and HSiEt3
(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room temperature.Instead
Liquid is answered to be concentrated, column chromatographs to obtain product(eluent is the same as embodiment 1 by 239mg.) yield 89%.1H
NMR(CDCl3, 500MHz) and δ=7.86-7.77 (m, 4H), 7.70 (dd, J=8.5,1.8Hz, 1H), 7.49-7.42 (m, 2H),
7.07 (d, J=19.3Hz, 1H), 6.57 (d, J=19.3Hz, 1H), 1.02 (t, J=7.9Hz, 9H), 0.71 (q, J=
7.9Hz,6H)；13C NMR(CDCl3, 125MHz) and δ=144.8,135.9,133.6,133.3,128.2,128.1,127.7,
126.5,126.2,125.9,123.3,7.5,3.6.
Embodiment 6
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(189mg, 1.00mmol) and HSiEt3
(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room temperature.Instead
Liquid is answered to be concentrated, column chromatographs to obtain product218mg (eluent: petroleum ether: ethyl acetate=10:1) yield
72%.1H NMR(CDCl3, 500MHz) and δ=7.54 (dd, J=7.7,1.6Hz, 1H), 7.30 (d, J=19.5Hz, 1H),
7.27-7.24 (m, 1H), 7.06 (td, J=7.5,1.1Hz, 1H), 7.00 (dd, J=8.0,1.2Hz, 1H), 6.35 (d, J=
19.5Hz, 1H), 3.89-3.84 (m, 4H), 2.99-2.93 (m, 4H), 0.99 (t, J=7.9Hz, 9H), 0.67 (q, J=
7.9Hz,6H).13C NMR(CDCl3, 125MHz) and δ=150.1,142.3,133.1,128.6,126.9,125.7,123.1,
118.1,67.3,52.6,7.4,3.6.HRMS(ESI)calcd for C18H29KNOSi[M+K]+342.1650,found
342.1644.
Embodiment 7
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(148mg, 1.00mmol) and HSiEt3
(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room temperature.Instead
Liquid is answered to be concentrated, column chromatographs to obtain product(eluent is the same as embodiment 1 by 184mg.) yield 70%.1H NMR
(CDCl3, 500MHz) and δ=6.55 (d, J=19.1Hz, 1H), 5.84-5.79 (m, 1H), 5.64 (d, J=19.1Hz, 1H),
4.75-4.71(m,2H),2.38-2.08(m,5H),1.94-1.88(m,1H),1.75(s,3H),1.53-1.44(m,1H),
0.94 (t, J=7.9Hz, 9H), 0.59 (q, J=7.9Hz, 6H)13C NMR(CDCl3, 125MHz) and δ=149.8,147.9,
137.2,129.9,121.2,108.7,41.3,31.4,27.4,24.4,20.8,7.4,3.6.HRMS(ESI)calcd for
C17H31Si[M+H]+263.2190,found 263.2190.
Embodiment 8
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(166mg, 1.00mmol) and
HSiEt3(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room
Temperature.Reaction solution concentration, column chromatograph to obtain product174mg (eluent: petroleum ether: ethyl acetate
=20:1) yield 62%.1H NMR(CDCl3, 500MHz) and δ=7.57 (s, 1H), 7.14 (dd, J=3.5,0.9Hz, 1H),
6.49 (dd, J=3.5,1.7Hz, 1H), 6.02 (dt, J=18.7,6.3Hz, 1H), 5.71 (d, J=18.7Hz, 1H), 4.36
(t, J=6.9Hz, 2H), 2.60-2.54 (m, 2H), 0.90 (t, J=7.9Hz, 9H), 0.53 (q, J=7.9Hz, 6H)；13C
NMR(CDCl3, 125MHz) and δ=146.2,142.6,130.0,117.8,111.8,63.8,36.2,7.3,3.4.HRMS (ESI)
calcd for C15H24NaO3Si[M+Na]+303.1387,found 303.1392.
Embodiment 9
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(84mg, 1.00mmol) and HSiEt3
(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room temperature.Instead
Liquid is answered to be concentrated, column chromatographs to obtain product(eluent is the same as embodiment 1 by 145mg.) yield 73%.1H NMR
(CDCl3, 500MHz) and δ=6.03 (dt, J=18.6,6.3Hz, 1H), 5.53 (d, J=18.6Hz, 1H), 2.15-2.09 (m,
2H), 1.40-1.28 (m, 2H), 0.92 (t, J=7.9Hz, 9H), 0.91-0.88 (m, 3H), 0.54 (q, J=7.9Hz, 6H)；13C NMR(CDCl3, 125MHz) and δ=148.8,125.5,36.8,31.0,22.2,14.0,7.4,3.5.
Embodiment 10
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(216mg, 1.00mmol) and
HSiEt3(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room
Temperature.Reaction solution concentration, column chromatograph to obtain product222mg (eluent: petroleum ether: ethyl acetate
=20:1) yield 67%.1H NMR(CDCl3, 500MHz) and δ=7.29 (t, J=7.5Hz, 2H), 7.21 (t, J=7.3Hz,
1H), 7.10 (d, J=6.9Hz, 2H), 6.01 (dt, J=18.1,6.3Hz, 1H), 5.70 (dd, J=18.1,1.4Hz, 1H),
4.19 (t, J=6.8Hz, 2H), 2.56-2.52 (m, 1H), 2.49 (q, J=6.8Hz, 2H), 1.93-1.88 (m, 1H), 1.63-
1.58 (m, 1H), 1.34-1.29 (m, 1H), 0.93 (t, J=8.0Hz, 9H), 0.56 (q, J=8.0Hz, 6H)；13C NMR
(CDCl3, 125MHz) and δ=173.3,142.9,140.0,129.5,128.4,126.4,126.1,63.6,36.1,26.1,
24.1,17.0,7.3,3.4.HRMS(ESI)calcd for C20H31O2Si[M+H]+331.2088,found 331.2091.
Embodiment 11
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.4mL) stirs 1h under conditions of 80 DEG C, is then added(300mg, 1.00mmol) and
HSiEt3(116mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room
Temperature.Reaction solution concentration, column chromatograph to obtain product195mg (eluent: petroleum ether: acetic acid second
Ester=20:1) yield 47%.1H NMR(CDCl3, 500MHz) and δ=6.20 (dt, J=18.7,6.8 Hz, 1H), 5.72 (dt, J
=18.7,1.3Hz, 1H), 5.39 (s, 1H), 2.40-2.34 (m, 1H), 2.31-2.25 (m, 1H), 2.22-2.17 (m, 1H),
2.06-1.90 (m, 6H), 1.85-1.75 (m, 2H), 1.70-1.65m, 2H), 1.50 (dt, J=12.2,3.6Hz, 1H),
1.38-1.18 (m, 8H), 1.11-1.05 (m, 1H), 0.95-0.91 (m, 12H), 0.56 (q, J=7.9Hz, 6H)13C NMR
(CDCl3, 125MHz) and δ=144.5,140.5,132.0,119.9,82.4,50.3,49.6,46.4,45.2,42.0,41 .8,
35.5,35.0,31.9,31.8,28.8 26.0,25.5,23.7,22.1,14.4,7.4,3.5.HRMS(ESI)calcd for
C27H46KOSi[M+K]+453.2950,found453.2942.
Embodiment 12
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(118mg, 1.00mmol) and HSi
(OEt)3(164mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, is cooled to room
Temperature.Reaction solution concentration, column chromatograph to obtain product143mg (eluent: petroleum ether: ethyl acetate=
50:1) yield 51%.1H NMR(CDCl3, 500MHz) and δ=7.47 (d, J=8.1Hz, 2H), 7.33 (d, J=19.3Hz, 1H),
7.25 (d, J=8.3Hz, 2H), 6.21 (d, J=19.3Hz, 1H), 3.98 (q, J=7.0Hz, 6H), 2.45 (s, 3H), 1.36
(t, J=7.0Hz, 9H)；13C NMR(CDCl3, 125MHz) and δ=149.1,138.7,134.9,129.2,126.7,116.2,
58.6,21.3,18.3.
Embodiment 13
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(118mg, 1.00mmol) and(222mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, cold
But to room temperature.Reaction solution concentration, column chromatograph to obtain product248mg (eluent: petroleum ether: second
Acetoacetic ester=50:1) yield 73%.1H NMR(CDCl3, 500MHz) and δ=7.36 (d, J=7.8Hz, 2H), 7.16 (d, J=
7.8Hz, 2H), 6.95 (d, J=19.2Hz, 1H), 6.22 (d, J=19.2Hz, 1H), 2.36 (s, 3H), 0.20 (s, 3H),
0.15(s,18H)；13C NMR(CDCl3, 125MHz) and δ=144.9,138.1,135.4,129.2,126.5,125.3,21.2,
1.9,0.0.
Embodiment 14
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(118mg, 1.00mmol) and(142mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, cold
But to room temperature.Reaction solution concentration, column chromatograph to obtain product199mg (the same embodiment of eluent
1.) yield 77%.1H NMR(CDCl3, 500MHz) and δ=7.36 (d, J=7.9Hz, 2H), 7.15 (d, J=7.9Hz, 2H),
6.85 (d, J=19.1Hz, 1H), 6.41 (d, J=19.1Hz, 1H), 2.36 (s, 3H), 1.78-1.71 (m, 5H), 1.28-
1.10(m,5H),0.75-0.67(m,1H),0.12(s,6H)；13C NMR(CDCl3, 125MHz) and δ=144.2,137.7,
135.7,129.2,126.2,126.2,28.1,27.5,27.0,25.9,21.2,5.1.HRMS(ESI)calcd for
C17H26NaSi[M+Na]+281.1696,found 281.1690.
Embodiment 15
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (0.2mL) stirs 1h under conditions of 80 DEG C, is then added(118mg, 1.00mmol) and(172mg, 1.00mmol), the reaction was continued under conditions of 140 DEG C for reaction system for 24 hours, after reaction, cooling
To room temperature.Reaction solution concentration, column chromatograph to obtain product(eluent is the same as embodiment 1 by 251mg.) produce
Rate 87%.1H NMR(CDCl3, 500MHz) and δ=7.34 (d, J=7.9Hz, 2H), 7.14 (d, J=7.9Hz, 2H), 6.85 (d, J
=19.1Hz, 1H), 6.40 (d, J=19.1Hz, 1H), 2.35 (s, 3H), 1.36-1.24 (m, 12H), 0.89 (t, J=
6.8Hz,3H),0.65-0.60(m,2H),0.13(s,6H).13C NMR(CDCl3, 125MHz) and δ=143.7,137.7,
135.7,129.2,127.3,126.2,33.6,31.9,29.3,29.3,23.9,22.7,21.2,15.7,14.1,-
3.0.HRMS(ESI)calcd for C19H32NaSi[M+Na]+311.2165,found 311.2163.
Embodiment 16
Decacarbonyldimanganese (57mg, 0.15mmol) is added in dry tube sealing, ligand 1 (129mg, 0.30mmol) and trifluoro
Toluene (5mL) stirs 1h under conditions of 80 DEG C, is later transferred to reaction mixture in the autoclave of one 50mL, adds
Enter(450mg, 3.00mmol) is filled with butylene into kettle and empties three times, be finally filled with the propylene of 0.45Mpa, instead
It answers system to react 24 hours under conditions of 115 DEG C, after reaction, is cooled to room temperature.Reaction solution concentration, column, which chromatographs, to be produced
Object(eluent is the same as embodiment 1 by 428mg.) yield 75% (dehydrogenation silication product: hydrogen silication product > 99:1).1H NMR(CDCl3, 500MHz) and δ=7.21 (t, J=7.4Hz, 2H), 7.07 (t, J=7.4Hz, 1H), 7.01 (t, J=
7.4Hz, 2H), 6.06 (dq, J=18.5,6.2Hz, 1H), 5.64 (dq, J=18.5,1.7Hz, 1H), 2.12 (s, 2H), 1.82
(dd, J=6.2,1.7Hz, 3H), 0.03 (s, 6H)13C NMR(CDCl3, 125MHzj) and δ=143.3,140.2,129.4,
128.2,128.0,123.8,26.2,22.6,-3.3.HRMS(ESI)calcd for C12H19Si[M+H]+191.1251,
found 191.1256.
Embodiment 17
Decacarbonyldimanganese (19mg, 0.05mmol) is added in dry tube sealing, ligand 1 (43mg, 0.10mmol) and trifluoro
Toluene (5mL) stirs 1h under conditions of 80 DEG C, is later transferred to reaction mixture in the autoclave of one 50mL, adds
Enter(150mg, 1.00mmol) is filled with butylene into kettle and empties three times, be finally filled with the butylene of 0.20Mpa, instead
It answers system to react 24 hours under conditions of 115 DEG C, after reaction, is cooled to room temperature.Reaction solution concentration, column, which chromatographs, to be produced
Object(eluent is the same as embodiment 1 by 104mg.) yield 51% (dehydrogenation silication product: hydrogen silication product > 99:
1)。1H NMR(CDCl3, 500MHz) and δ=7.22 (t, J=7.7Hz, 1H), 7.08 (t, J=7.4Hz, 1H), 7.01 (d, J=
6.7Hz, 2H), 6.09 (dt, J=18.6,5.8Hz, 1H), 5.61 (dt, J=18.6,1.7Hz, 1H), 2.13 (s, 2H), 1.01
(t, J=7.5Hz, 3H), -0.04 (s, 6H)13C NMR(CDCl3, 125MHz) and δ=150.0,140.2,128.2,128.0,
126.1,123.8,29.4,26.3,12.8,-3.3.HRMS(ESI)calcd for C13H20KSi[M+K]+243.0966,
found 243.0964.
Claims (7)
1. a kind of method that selectivity prepares alkenyl silanes, it is characterized in that: it is with terminal olefin (1) and trisubstituted silane
(2) it, at 115-160 DEG C, is reacted 24-36 hours under the action of ligand 1, with single for raw material using benzotrifluoride as solvent
Selectivity obtains the dehydrogenation silication product (3) of anti-configuration, and the ligand 1 is just like flowering structure:
2. preparation method according to claim 1, it is characterized in that: the terminal olefin (1) is ethylene, propylene and fourth
Alkene or activated olefins or disactivation alkene or some terminal olefins containing labyrinth with various substituent groups.
3. preparation method according to claim 1, it is characterized in that: the R base of the trisubstituted silane (2) can be identical
Or it is not identical.
4. preparation method according to claim 1, it is characterized in that: the R base of the trisubstituted silane (2) be ethyl,
Ethyoxyl, trimethylsiloxy group, alkyl or cycloalkyl.
5. preparation method according to claim 1, it is characterized in that: the reaction condition is not required under air conditions
Want extra padding inert gas.
6. preparation method according to claim 1, it is characterized in that: the molar ratio of the terminal olefin and three substituted silanes
It is 1:1.
7. preparation method according to claim 1, it is characterized in that: when preparing dehydrogenation silication product, ten carbonyl of catalyst
The dosage of two manganese is the 5% of terminal olefin (1) molal quantity, and the dosage of ligand 1 is the 10% of terminal olefin (1) molal quantity.
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| JP3049316B1 (en) * | 1999-03-09 | 2000-06-05 | 工業技術院長 | Method for producing alkenylsilanes |
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| CN106661059A (en) * | 2014-09-02 | 2017-05-10 | 加州理工学院 | Base-catalyzed silylation of terminial alkyne c-h bonds |
| CN109021003A (en) * | 2018-07-06 | 2018-12-18 | 华侨大学 | A kind of vinyl silicon germanium stannane derivative preparation method |
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2019
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| JP3049316B1 (en) * | 1999-03-09 | 2000-06-05 | 工業技術院長 | Method for producing alkenylsilanes |
| CN103588804A (en) * | 2012-08-16 | 2014-02-19 | 莫门蒂夫性能材料股份有限公司 | Dehydrogenative silylation and crosslinking using cobalt catalysts |
| CN105229016A (en) * | 2013-05-06 | 2016-01-06 | 莫门蒂夫性能材料股份有限公司 | By the saturated and unsaturated silahydrocarbons of the olefinic silane of iron and the catalysis of cobalt pyridine diimine |
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