CN110229180B - Method for selectively preparing alkenyl silane - Google Patents
Method for selectively preparing alkenyl silane Download PDFInfo
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- CN110229180B CN110229180B CN201910640507.6A CN201910640507A CN110229180B CN 110229180 B CN110229180 B CN 110229180B CN 201910640507 A CN201910640507 A CN 201910640507A CN 110229180 B CN110229180 B CN 110229180B
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- 229910000077 silane Inorganic materials 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title claims abstract description 9
- -1 alkenyl silane Chemical compound 0.000 title claims description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003446 ligand Substances 0.000 claims abstract description 28
- 150000001336 alkenes Chemical group 0.000 claims abstract description 20
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 150000004756 silanes Chemical class 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 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 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 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 1
- 238000006884 silylation reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 24
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- 239000003480 eluent Substances 0.000 description 18
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 17
- 238000004440 column chromatography Methods 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 11
- 239000003208 petroleum Substances 0.000 description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019443 NaSi Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001343 alkyl silanes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 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
- 238000002444 silanisation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 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
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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
- C07F7/18—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
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- 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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Abstract
A method for realizing selective silylation of terminal olefin by ligand regulation is characterized in that terminal olefin and trisubstituted silane are used as raw materials, trifluorotoluene is used as a solvent, and the reaction is carried out for 24 hours at 140 ℃ under the action of ligand 1, so that a trans-configuration dehydrosilicification product is obtained in a single selectivity mode.
Description
Technical Field
A method for selectively preparing an alkenyl silane.
Background
Organic silicon is used as an important chemical raw material and widely applied to the fields of buildings, electronic industry, medicines, foods and the like [ see: (a) silicon,2009,1,147, (b) chem.rev.,2010,110,1233, (c) chem.soc.rev.,2011,40,696 ]. Although the preparation of such compounds using transition metal catalysis has been well reported [ see: (a) nat. rev. chem.,2018,2,15.(b) Science,2002,298,204.(c) RSC adv.,2015,5,20603.], but there are several problems in general with the silylation reaction of olefins, that (i) reaction by-products are large; secondly, the hydrogen silication product is mainly used, and the high-efficiency synthesis of the dehydrosilicification product is rarely reported; the applicability of the substrate is poor; and fourthly, in the dehydrosilicification reaction, an extra hydrogen acceptor or an oxidant is needed, and the atom economy is poor. Meanwhile, manganese is used as a nontoxic and environment-friendly metal, is rich in earth crust, shows good water and oxygen tolerance compared with other low-valence metals such as Fe, Co, Ni and the like, and a recently reported manganese-catalyzed synthesis strategy mainly relates to a hydrogen hydrogenation reaction of olefin. Dehydrosilicidation reacts with moderate selectivity with some activated olefins and silanes with large chemical resistance, but with poor compatibility with non-activated olefins and complex molecules and other classes of silanes [ see: (a) chen.j.chem., 2018,36,1047, (b) chem.asian, 2018,13,2307. Therefore, the development of an efficient synthetic method for preparing alkenylsilanes and alkylsilanes with high selectivity has been the focus of research in this field. Under the condition of not adding any additive, the silanization reaction of various types of olefins including gases such as ethylene, propylene and the like is realized only by regulating and controlling the ligand, and the synthetic method is simple and efficient and has great industrial application potential.
Disclosure of Invention
The technical problem to be solved by the invention is to realize the selective silylation reaction of olefin by regulating and controlling the ligand and the application thereof.
The synthetic route of the invention is as follows:
a selective preparation method of alkenyl silane, it takes terminal olefin (1) and trisubstituted silane (2) as raw materials, take trifluorotoluene as solvent, react for 24-36 hours under the influence of ligand 1 at 115-:
in the above preparation method, the terminal olefin (1) may be ethylene, propylene and butylene or activated olefin or non-activated olefin with various substituents and some terminal olefins containing complex structures.
In the above preparation method, the R groups of the trisubstituted silane (2) can be the same or different.
In the preparation method, the R group of the trisubstituted silane (2) can be ethyl, ethoxy, trimethylsiloxy, alkyl or cycloalkyl.
In the preparation method, the reaction condition is under the air condition, and no inert gas needs to be additionally filled.
In the preparation method, the mol ratio of the terminal olefin to the tri-substituted silane is 1: 1.
In the above production method, in the production of the dehydrosilicidation product, the catalyst decacarbonyldimanganese is used in an amount of 5 mol% based on the terminal olefin (1), and the ligand 1 is used in an amount of 10 mol% based on the terminal olefin (1).
A typical reaction is as follows:
the method disclosed by the invention is simple and efficient, high in selectivity, strong in substrate applicability and high in raw material utilization rate, especially initially realizes single selectivity under ligand regulation in the direction of dehydrosilicification, and avoids the problems of quality reduction and difficult separation caused by introduction of byproducts in the industrial application process.
Detailed Description
Ligand 1 was synthesized according to the literature (adv. synth. catal.2015,357, 3538).
The following examples are used to aid understanding of the present invention, but are not intended to limit the scope of the present invention.
Example 1
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(118mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
191mg (eluent: petroleum ether, 60-90 ℃ C.) yield 82%.1H NMR(CDCl3,500MHz)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)δ＝144.7,137.8,135.9,129.2,126.2,124.5,21.2,7.4,3.6.
Example 2
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(110mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
164mg (eluent, same as example 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)δ＝145.5,137.4,127.4,125.8,125.4,124.6,7.4,3.5.
Example 3
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(162mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
233mg (eluent: petroleum ether: ethyl acetate ═ 20:1) yield 84%.1HNMR(CDCl3,500MHz)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)δ＝169.5,150.3,143.7,136.4,127.3,126.3,121.6,21.2,7.4,3.5.
Example 4
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(138mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
195mg (eluent same as example 1.) yield 77%.1H NMR(CDCl3,500MHz)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)δ＝143.4,137.0,133.5,128.6,127.5,126.9,7.4,3.5.
Example 5
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(154mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
239mg (eluent same as example 1.) yield 89%.1H NMR(CDCl3,500MHz)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)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.
Example 6
Dry sealsTo the tube were added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(189mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
Yield of 218mg (eluent: petroleum ether: ethyl acetate ═ 10:1) 72%.1H NMR(CDCl3,500MHz)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)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.
Example 7
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(148mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
184mg (eluent same as example 1.) yield 70%.1H NMR(CDCl3,500MHz)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)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.
Example 8
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(166mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
Yield 62% of 174mg (eluent: petroleum ether: ethyl acetate ═ 20: 1).1H NMR(CDCl3,500MHz)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)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.
Example 9
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(84mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
145mg (eluent same as that of the eluent)Example 1. ) The yield was 73%.1H NMR(CDCl3,500MHz)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)δ＝148.8,125.5,36.8,31.0,22.2,14.0,7.4,3.5.
Example 10
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(216mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
Yield of 222mg (eluent: petroleum ether: ethyl acetate ═ 20:1) 67%.1H NMR(CDCl3,500MHz)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)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.
Example 11
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.4mL) and stirred at 80 ℃ for 1h, followed by addition
(300mg,1.00mmol) and HSiEt3(116mg,1.00mmol), the reaction system continues to react for 24h at 140 ℃, and the reaction is finishedAfter that, it was cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
195mg (eluent: petroleum ether: ethyl acetate ═ 20:1) yield 47%.1H NMR(CDCl3,500MHz)δ＝6.20(dt,J＝18.7,6.8Hz,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)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.
Example 12
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(118mg,1.00mmol) and HSi (OEt)3(164mg,1.00mmol), the reaction was continued at 140 ℃ for 24h, and after completion of the reaction, it was cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
143mg (eluent: petroleum ether: ethyl acetate 50:1) yield 51%.1H NMR(CDCl3,500MHz)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)δ＝149.1,138.7,134.9,129.2,126.7,116.2,58.6,21.3,18.3.
Example 13
To the dried sealed tube were added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and the mixture was stirred at 80 deg.CFor 1h, then adding
(118mg,1.00mmol) and
(222mg,1.00mmol), the reaction was continued at 140 ℃ for 24h, and after completion of the reaction, it was cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
248mg (eluent: petroleum ether: ethyl acetate 50:1) yield 73%.1H NMR(CDCl3,500MHz)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)δ＝144.9,138.1,135.4,129.2,126.5,125.3,21.2,1.9,0.0.
Example 14
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(118mg,1.00mmol) and
(142mg,1.00mmol), the reaction system is continued to react at 140 ℃ for 24h, and after the reaction is finished, the reaction system is cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
199mg (eluent same as example 1.) yield 77%.1H NMR(CDCl3,500MHz)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)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.
Example 15
To the dried sealed tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (0.2mL) and stirred at 80 ℃ for 1h, followed by addition
(118mg,1.00mmol) and
(172mg,1.00mmol), the reaction was continued at 140 ℃ for 24h, and after completion of the reaction, the reaction was cooled to room temperature. Concentrating the reaction solution, and performing column chromatography to obtain the product
251mg (eluent as in example 1.) yield 87%.1H NMR(CDCl3,500MHz)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)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.
Example 16
To the dried lock tube was added dimanganese decacarbonyl (57mg,0.15mmol), ligand 1(129mg,0.30mmol) and trifluorotoluene (5mL) and stirred at 80 ℃ for 1h, after which the reaction mixture was transferred to a 50mL autoclave and added
(450mg,3.00mmol), filling butylene into the kettle and emptying for three times, finally filling propylene of 0.45Mpa, reacting the reaction system at 115 ℃ for 24 hours, and cooling to room temperature after the reaction is finished. Concentrating the reaction solution, and performing column chromatography to obtain the product
428mg (eluent as in example 1.) yield 75% (dehydrosilicification product: hydrosilicidation product)>99:1)。1H NMR(CDCl3,500MHz)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)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.
Example 17
To the dried lock tube was added dimanganese decacarbonyl (19mg,0.05mmol), ligand 1(43mg,0.10mmol) and trifluorotoluene (5mL) and stirred at 80 ℃ for 1h, after which the reaction mixture was transferred to a 50mL autoclave and added
(150mg,1.00mmol), filling butylene into the kettle and emptying for three times, finally filling butylene of 0.20Mpa, reacting the reaction system at 115 ℃ for 24 hours, and cooling to room temperature after the reaction is finished. Concentrating the reaction solution, and performing column chromatography to obtain the product
104mg (eluent as in example 1.) yield 51% (dehydrosilicidation product: hydrosilation product)>99:1)。1H NMR(CDCl3,500MHz)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)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 (3)
1. A method for selectively preparing alkenyl silane is characterized in that: it is a terminal olefin and a trisubstituted silane R3SiH is used as a raw material, benzotrifluoride is used as a solvent, and the reaction is carried out for 24 to 36 hours at the temperature of 115-160 ℃ under the action of a ligand 1 and a catalyst of manganese decacarbonyl, so as to obtain a dehydrosilicification product with a trans-configuration in a single selectivity, R groups of the tri-substituted silane can be the same or different, and the R group of the tri-substituted silane is ethyl, ethoxy, trimethylsiloxy, methyl, benzyl or cyclohexyl;
the ligand 1 has the following structure:
2. the method of claim 1, wherein: the molar ratio of the terminal olefin to the tri-substituted silane is 1: 1.
3. The method of claim 1, wherein: in the preparation of the dehydrosilicidation product, the catalyst decacarbonyl dimanganese was used in an amount of 5 mole% of the terminal olefin and the ligand 1 was used in an amount of 10 mole% of the terminal olefin.
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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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| 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 |
| CN106661059A (en) * | 2014-09-02 | 2017-05-10 | 加州理工学院 | Base-catalyzed silylation of terminial alkyne c-h bonds |
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