CN106083908A - A kind of method synthesizing α alkenyl silanes compounds - Google Patents
A kind of method synthesizing α alkenyl silanes compounds Download PDFInfo
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- CN106083908A CN106083908A CN201610390530.0A CN201610390530A CN106083908A CN 106083908 A CN106083908 A CN 106083908A CN 201610390530 A CN201610390530 A CN 201610390530A CN 106083908 A CN106083908 A CN 106083908A
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- alkenyl silanes
- alkynes
- silanes compounds
- silane
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- -1 alkenyl silanes compounds Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 30
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 5
- 150000001345 alkine derivatives Chemical class 0.000 claims abstract description 27
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910000077 silane Inorganic materials 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- 238000004809 thin layer chromatography Methods 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 5
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229910052740 iodine Inorganic materials 0.000 claims description 5
- 125000003107 substituted aryl group Chemical group 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000003368 amide group Chemical group 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229930192474 thiophene Natural products 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 150000003233 pyrroles Chemical class 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229930195733 hydrocarbon Natural products 0.000 claims 1
- 150000002430 hydrocarbons Chemical class 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052763 palladium Inorganic materials 0.000 abstract description 3
- 229910052703 rhodium Inorganic materials 0.000 abstract description 3
- 239000010948 rhodium Substances 0.000 abstract description 3
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 125000000524 functional group Chemical group 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 230000007096 poisonous effect Effects 0.000 abstract description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 229910052723 transition metal Inorganic materials 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 18
- 238000005160 1H NMR spectroscopy Methods 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 9
- BPYFPNZHLXDIGA-UHFFFAOYSA-N diphenylsilicon Chemical compound C=1C=CC=CC=1[Si]C1=CC=CC=C1 BPYFPNZHLXDIGA-UHFFFAOYSA-N 0.000 description 9
- 238000005984 hydrogenation reaction Methods 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 238000004440 column chromatography Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 0 CCC(C1)N1c1cc(N)c(CC=C(C)c2cccc(C3=*(C)[C@@](C)C(C)(*)O3)*2[*+](C)*)c(C)c1 Chemical compound CCC(C1)N1c1cc(N)c(CC=C(C)c2cccc(C3=*(C)[C@@](C)C(C)(*)O3)*2[*+](C)*)c(C)c1 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 238000002512 chemotherapy Methods 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 1
- 241000819038 Chichester Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- 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
- C07F7/0896—Compounds with a Si-H linkage
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a kind of method synthesizing α alkenyl silanes compounds, with alkynes as raw material, with silane for silicon source, with CoX2OIP complex is catalyst, in the presence of sodium triethylborohydride, at a temperature of 30 DEG C～80 DEG C, reacts 5 seconds～30 minutes prepared alkenyl silanes, alkynes, silane, CoCl2OIP complex, the mol ratio of sodium triethylborohydride are 1:1:0.0005 0.02:0.0015 0.06；Compared with the conventional method, the method is applicable to the alkynes of number of different types, and reaction condition is gentle, easy and simple to handle, Atom economy 100%.It addition, reaction is without the addition of other any poisonous transition metal (such as ruthenium, rhodium, palladium etc.) salts, pharmaceutical synthesis has bigger actual application value.And functional group's tolerance of reaction is good, regioselectivity is the highest, generally 90:10 > 99:1.
Description
Technical field
This method relates to chemical synthesis process, specifically, is a kind of high chemo-selective, regioselectivity and three-dimensional choosing
The method of selecting property synthesis α-alkenyl silanes compounds.
Background technology
Organosilan is a class very important synthesis unit [a) In Chemistry at organic synthesis and Material Field
ofOrganic Silicon Compounds；Rappoport,Z.,Apeloig,Y.,Eds.；Wiley:Chichester,
1998,p 1687].Wherein, alkenyl silanes is the intermediate that a class is highly useful, it is possible to serve as stable thiazolinyl anion or
Thiazolinyl cation synthon [a) Chem.Rev.1986,86,857.].The hydrogenation of alkynes silicon is a kind of to meet the straight of atom economy
It is bonded into the method [a) Angew.Chem., Int.Ed.2004,43,2749.] of alkenyl silanes.But, high selective synthesis
α-alkenyl silanes only has several little reports, and the catalyst wherein used is noble metal complexes (Ru, Rh, Pd etc.)
[a)J.Am.Chem.Soc.2001,123,12726.b)Org.Lett.2000,2,1887.c)Org.Lett.2002,4,
2825.d)J.Org.Chem.2005,70,10717.].Up to the present, the high selectivity α silicon of the alkynes of cheap metal catalysis
Hydrogenation method it is not yet reported that.
Therefore, the silicon hydrogenation of the alkynes of the high selective cheap metal catalysis of development high efficiency synthesizes α-thiazolinyl silicon
Alkane has great meaning.
Summary of the invention
The problem to be solved in the present invention is to provide a kind of method of effective synthesis alkenyl silanes compounds, be by
CoX2-OIP complex catalysis alkynes geneva silicon hydrogenation, high chemo-selective, high regioselectivity, highly-solid selectively close
The method becoming alkenyl silanes compounds.
The present invention is achieved through the following technical solutions:
The invention discloses a kind of method synthesizing alkenyl silanes compounds, with alkynes as raw material, with silane for silicon source,
With CoX2-OIP complex is catalyst, in the presence of sodium triethylborohydride, at a temperature of-30 DEG C～80 DEG C, reacts 5 seconds～30
Minute prepared alkenyl silanes, alkynes, silane, CoCl2-OIP complex, the mol ratio of sodium triethylborohydride are 1:1:
0.0005-0.02:0.0015-0.06；
The structural formula of alkynes isR1, R2Being optionally aryl, heteroaryl, alkyl, hydrogen, aryl is optionally for taking
The aryl in generationSubstituted 1-naphthyl2-naphthylHeterocycle virtue
BaseY is any one in N, O, S, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15,
R16, R17, R18, R19, R20, R21, R22, R23, R24Optionally from H, halogen, C1-C16Alkyl, C1-C16Oxyl, sulfenyl, ammonia
Base, amido, thiophene, any one in pyrroles, X is F, Cl, Br, I, OAc, CF3SO3In any one.
As improving further, its structural formula of silane of the present invention isWherein R30, R31, R32Optionally
For hydrogen, alkyl, alkoxyl, substituted aryl, substituted heteroaryl.
As improving further, CoX of the present invention2The structural formula of-OIP complex is optically pure following chemical combination
Thing or its enantiomer or raceme, R25, R26, R27, R28, R29Optionally from C1-C16Alkyl, naphthyl, substituted aryl, benzyl:
X is F, Cl, Br, I, OAc, CF3SO3In any one.
As improving further, synthetic method of the present invention has the participation of organic solvent, described organic solvent
Be benzene, carbon tetrachloride, toluene, oxolane, ether, dichloromethane, acetonitrile, dioxane, petroleum ether, hexamethylene, normal hexane,
Ethyl acetate, chloroform, N, any one in N-diformamide.
As improving further, synthetic method of the present invention is not added with any solvent.
As improving further, alkynes of the present invention, silane, CoX2-OIP complex, sodium triethylborohydride
Mol ratio be 1:1:0.004-0.02:0.012-0.06.
As improving further, in synthetic method of the present invention, reaction temperature is-10 DEG C～40 DEG C.
As improving further, in synthetic method of the present invention, reaction temperature is 20 DEG C, and the response time is 5 minutes
Or 20 minutes.
As improving further, the product of gained of the present invention is to steam through recrystallization, thin layer chromatography, column chromatography or decompression
Evaporate to be separated and form.
Beneficial effects of the present invention is as follows:
Present approach provides a kind of effective by CoX2-OIP complex is catalyst, the hydrogenation of alkynes silicon synthesize
The method of alkenyl silanes compounds.Compared with the conventional method, the method is applicable to the alkynes of number of different types, reaction condition
Gentleness, easy and simple to handle, Atom economy 100%.It addition, react without other any poisonous transition metal (such as ruthenium, rhodium, palladium
Deng) addition of salt, pharmaceutical synthesis has bigger actual application value.And functional group's tolerance of reaction is good, region
Selectivity is the highest, generally 90:10-> 99:1.
Detailed description of the invention
The method of the present invention is a kind of effectively by the method for alkynes synthesis alkenyl silanes compounds.The method is to use
CoX2-OIP complex is as the synthesis alkenyl silanes of catalyst high regioselectivity.
The general molecular formula of the alkenyl silanes compounds synthesized by the inventive method is:R1, R2Permissible
Optionally from aryl, heteroaryl, alkyl, hydrogen, aryl is optionally from substituted arylSubstituted 1-naphthyl2-naphthylHeterocyclic aryl(Y is in N, O, S
Any one)；Wherein, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16, R17, R18, R19, R20, R21,
R22, R23, R24Optionally from H, halogen, C1-C16Alkyl, C1-C16Oxyl, sulfenyl, amino, amido, thiophene, Bi Kazhong
Any one, X is F, Cl, Br, I, OAc, CF3SO3In any one.Above-mentioned alkyl can be alkyl, cycloalkyl, benzyl
Base.
The alkenyl silanes compounds of the present invention is with alkynes as raw material, and diphenyl silane is silicon source, at boron triethyl hydrogen
In the presence of changing sodium, it is solvent at oxolane, with CoX2-OIP complex prepares as catalyst reaction, available following formula table
Show:
The structural formula of alkynes is:Wherein, R1, R2As previously mentioned；The general structure of catalyst is (for appointing
Optically pure structure of anticipating or its enantiomer or raceme, do not limited by diagram)
R25, R26, R27, R28, R29Optionally from C1-C16Alkyl, naphthyl, substituted aryl, benzyl.
Described alkynes, diphenyl silane, CoX2-OIP complex, the mol ratio of sodium triethylborohydride are 1:1:
0.0005-0.05:0.0015-0.15；1:1:0.004-0.0:2:0.012-0.06 further.Reaction temperature is recommended as-30 DEG C
～80 DEG C, it is further recommended that-10 DEG C～40 DEG C, it is particularly recommended that 20 DEG C.Response time is recommended as 3 minutes-48 hours, pushes away further
Recommend is 5 seconds-20 minutes, it is particularly recommended that 5 minutes.Wherein, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14, R15, R16,
R17, R18, R19, R20, R21, R22, R23, R24, R25, R26, R27, R28, R29As previously mentioned.
The alkyl mentioned in the present invention, the group all recommending carbon number to be 1～16, it is further recommended that carbon number is 1～10, especially
Recommending carbon number is 1～6.The cycloalkyl that the present invention mentions, the group all recommending carbon number to be 3～16, it is further recommended that carbon number is 3
～10, it is particularly recommended that carbon number is 3～6.The aryl that the present invention mentions, refers both to phenyl, naphthyl and contains N, the heteroaryl of O, S.
The reaction of the inventive method can be carried out under solvent-free, it is also possible to is carrying out in polarity or non-polar solven,
As benzene, carbon tetrachloride, toluene, oxolane, ether, dichloromethane, acetonitrile, dioxane, petroleum ether, hexamethylene, normal hexane,
Ethyl acetate, chloroform, N, N-diformamide etc..
The inventive method can be passed through recrystallization, thin layer chromatography, column chromatography or decompression distillation and be separated.The inventive method
Provide the synthetic method of some new thiazolinyl silicon.
Below by specific embodiment, technical scheme is illustrated further:
Embodiment 1:CoX2The silicon hydrogenation of the terminal alkyne of-OIP complex catalysis
20 DEG C, under condition of nitrogen gas, in a reaction tube being dried, it is sequentially added into CoX2-OIP complex (0.02mmol),
Oxolane (2ml), diphenyl silicon hydrogen (1.0mmol), it is injected into sodium triethylborohydride (0.06mmol), alkynes
(1.0mmol) after, then stirring 5 minutes, column chromatography for separation obtains product.P1:Diphenyl (1-phenylvinyl) silane
White solid, 86% productivity.M.P.:59～60 DEG C of .IR (cm-1):3063,2127,1491,1429,1113.1H
NMR(CDCl3,400MHz):δ7.51-7.61(m,4H),7.30-7.45(m,8H),7.17-7.29(m,3H),6.25-6.32
(m,1H),5.66-5.72(m,1H),5.37-5.42(m,1H)；13C NMR:(CDCl3,100MHz):δ145.9,142.9,
135.8,133.0,132.1,129.8,128.4,128.0,127.1,126.7.HRMS(EI)calculated for
[C20H18Si]+requires m/z 286.1178,found m/z 286.1181.
P2:Diphenyl (1-(p-tolyl) vinyl) silane
White solid, 96% productivity.M.P.:64～65 DEG C of .IR (cm-1):2919,2126,1565,1428,803.1H
NMR(CDCl3, 400MHz): δ 7.53-7.59 (m, 4H), 7.32-7.45 (m, 6H), 7.22-7.25 (m, 2H), 7.06 (d, J=
8.0Hz, 2H), 6.26 (d, J=2.4Hz, 1H), 5.63 (d, J=2.4Hz, 1H), 5.38 (s, 1H), 2.30 (s, 3H)；13C
NMR:(CDCl3,100MHz):δ145.4,139.9,136.8,135.8,133.2,131.3,129.7,129.1,128.0,
126.6,21.1.HRMS(EI)calculated for[C21H20Si]+requires m/z 300.1334,found m/z
300.1333.
P3:(1-(4-Bromophenyl) vinyl) diphenylsilane
White solid, 96% productivity.M.P.:84～85 DEG C of .IR (cm-1):3066,2129,1484,1429,1114.1H
NMR(CDCl3, 400MHz): δ 7.51-7.61 (m, 4H), 7.32=7.45 (m, 8H), 7.15-7.22 (m, 2H), 6.25 (d, J
=2.2Hz, 1H), 5.70 (d, J=2.2Hz, 1H), 5.36 (s, 1H)；13C NMR:(CDCl3,100MHz):δ145.0,
141.8,135.7,132.6,132.5,131.5,129.9,128.3,128.1,121.1.HRMS(EI)calculated for
[C20H17BrSi]+requires m/z 364.0283,found m/z 364.0286.
P4:(4-(1-(Diphenylsilyl) vinyl) phenyl) methanol
Colourless liquid, 65% productivity.IR(cm-1):3322,3017,2126,1428,1113.1H NMR(CDCl3,
400MHz): δ 7.56 (d, J=7.2Hz, 4H), 7.30-7.43 (m, 8H), 7.23 (d, J=7.2Hz, 2H), 6.28 (d, J=
2.0Hz, 1H), 5.68 (d, J=2.0Hz, 1H), 5.39 (s, 1H), 4.60 (s, 2H), 1.74 (brs, 1H)；13C NMR:
(CDCl3,100MHz):δ145.5,139.6,135.7,132.9,132.2,129.8,128.0,127.1,126.9,
65.0.HRMS(EI)calculated for[C21H20OSi]+requires m/z 316.1283,found m/z
316.1287.
P4:1-(4-(1-(Diphenylsilyl) vinyl) phenyl) ethanone
White solid, 85% productivity.M.P.:73～74 DEG C of .IR (cm-1):3066,2128,1681,1601,1114.1H
NMR(CDCl3, 400MHz): δ 7.90 (d, J=8.4Hz, 2H), 7.53-7.58 (m, 4H), 7.32-7.43 (m, 8H), 6.33
(d, J=2.4Hz, 1H), 5.79 (d, J=2.4Hz, 1H), 5.40 (s, 1H), 2.55 (s, 3H)；13C NMR:(CDCl3,
100MHz):δ197.6,147.9,145.5,135.7,133.8,132.4,130.0,128.5,128.1,126.9,
26.5.HRMS(EI)calculated for[C22H20OSi]+requires m/z 328.1283,found m/z
328.1282.
P5:Diphenyl (1-(thiophen-2-yl) vinyl) silane
-30 DEG C, under condition of nitrogen gas, in a reaction tube being dried, it is sequentially added into CoX2-OIP complex
(0.02mmol), oxolane (2ml), diphenyl silicon hydrogen (1.0mmol), it is injected into sodium triethylborohydride (0.06mmol),
Alkynes (1.0mmol), after then stirring 5 minutes, column chromatography for separation obtains product.White solid, 85% productivity.M.P.:54～55
℃.IR(cm-1):3067,2130,1484,1231,1114.1H NMR(CDCl3, 400MHz): δ 7.59 (d, J=7.2Hz,
4H), 7.33-7.45 (m, 6H), 7.12 (d, J=5.2Hz, 1H), 6.91 (d, J=3.6Hz, 1H), 6.86 (t, J=4.4Hz,
1H), 6.33 (s, 1H), 5.50 (d, J=1.6Hz, 1H), 5.41 (s, 1H)；13C NMR:(CDCl3,100MHz):δ146.3,
137.9,135.8,132.4,130.0,129.6,128.1,127.5,125.9,124.1.HRMS(EI)calculated for
[C18H16SSi]+requires m/z 292.0742,found m/z 292.0739.
Embodiment 2:CoX2The silicon hydrogenation of the non-end alkynes of-OIP complex catalysis
20 DEG C, under condition of nitrogen gas, in a reaction tube being dried, it is sequentially added into CoX2-OIP complex (0.02mmol),
Oxolane (2ml), diphenyl silicon hydrogen (1.0mmol), it is injected into sodium triethylborohydride (0.06mmol), alkynes
(1.0mmol) after, then stirring 5 minutes, column chromatography for separation obtains product.
P6:(E)-dec-5-en-5-yldiphenylsilane
Colourless liquid, 97% productivity.IR(cm-1):3002,2957,2116,11429,1111.1H NMR(CDCl3,
400MHz):δ7.52-7.59(m,4H),7.31-7.42(m,6H),5.86-5.93(m,1H),5.07(s,1H),2.13-2.26
(m,4H),1.18-1.42(m,8H),0.86-0.94(m,3H),0.76-0.83(m,3H).HRMS(EI)calculated for
[C22H30Si]+requires m/z 322.2117,found m/z 322.2119.
P7:(E)-diphenyl (1-phenylbut-1-en-1-yl) silane
White solid, 88% productivity.M.P.:47～48 DEG C of .IR (cm-1):2965,2123,1600,1429,1070.1H
NMR(CDCl3,400MHz):δ7.48-7.55(m,3H),7.30-7.42(m,6H),7.18-7.24(m,2H),7.10-7.17
(m, 1H), 6.95-7.01 (m, 2H), 6.19 (t, J=7.4Hz, 2H), 5.18 (s, 1H), 2.05-2.15 (m, 2H), 0.95 (t,
J=7.4Hz, 3H)；13C NMR:(CDCl3,100MHz):δ149.4,141.3,137.2,135.7,133.6,129.6,
128.3,128.0,127.9,125.8,23.6,14.0.HRMS(EI)calculated for[C22H22Si]+requires m/z
314.1491,found m/z 314.1495.
P8:(E)-(4,4-dimethylpent-2-en-2-yl) diphenylsilane
Colourless liquid, 89% productivity.IR(cm-1): 3067,2956,2117,1428,1112.1H NMR(CDCl3,
400MHz): δ 7.52-7.57 (m, 4H), 7.32-7.41 (m, 6H), 6.01 (q, J=1.8Hz, 1H), 4.98 (s, 1H), 1.90
(d, J=1.8Hz, 3H), 1.16 (s, 9H)；13C NMR:(CDCl3,100MHz):δ155.4,135.6,134.0,129.5,
128.9,127.9,35.1,30.6,16.3HRMS(EI)calculated for[C19H24Si]+requires m/z
280.1647,found m/z 280.1645.
P9:(E)-diphenyl (2-phenyl-1-(thiophen-2-yl) vinyl) silane
Colourless liquid, 68% productivity.1H NMR(CDCl3, 400MHz): δ 7.59 (dd, J=8.0,1.6Hz, 4H), 7.30-
7.39 (m, 6H), 7.15 (s, 5H), 7.04-7.09 (m, 2H), 6.79-6.85 (m, 1H), 6.66 (dd, J=3.6,1.2Hz,
1H),5.35(s,1H).Anal.Calcd for C24H20SSi:C,78.21；H,5.47.Found:C,77.75；H,5.63.
P10:(E)-(1,2-diphenylvinyl) diphenylsilane
80 DEG C, under condition of nitrogen gas, in a reaction tube being dried, it is sequentially added into CoX2-OIP complex (0.02mmol),
Oxolane (2ml), diphenyl silicon hydrogen (1.0mmol), it is injected into sodium triethylborohydride (0.06mmol), alkynes
(1.0mmol) after, then stirring 5 minutes, column chromatography for separation obtains product.Colourless liquid, 33% productivity.IR(cm-1):3062,
1595,1489,1429,1110.1H NMR(CDCl3,400MHz):δ7.51-7.60(m,4H),7.21-7.40(m,6H),
6.93-7.20(m,11H),5.28(s,1H)；13C NMR:(CDCl3,100MHz):δ142.9,141.6,140.2,136.9,
135.8,133.0,129.8,129.6,128.6,128.02,128.98,127.9,127.5,126.1.HRMS(EI)
calculated for[C26H22Si]+requires m/z 362.1491,found m/z 362.1489.
Finally, in addition it is also necessary to be only several specific embodiments of the present invention it is noted that listed above.Obviously, this
Bright it is not limited to above example, it is also possible to have many deformation.Those of ordinary skill in the art can be from present disclosure
The all deformation directly derived or associate, are all considered as protection scope of the present invention.
Claims (9)
1. the method synthesizing alkenyl silanes compounds, is characterized in that, with alkynes as raw material, with silane for silicon source, with
CoX2-OIP complex is catalyst, in the presence of sodium triethylborohydride, at a temperature of-30 DEG C～80 DEG C, reacts 5 seconds～30 points
Clock prepares alkenyl silanes, described alkynes, silane, CoCl2-OIP complex, the mol ratio of sodium triethylborohydride are 1:1:
0.0005-0.02:0.0015-0.06；
The structural formula of described alkynes isR1, R2Being optionally aryl, heteroaryl, alkyl, hydrogen, aryl is optionally
Substituted arylSubstituted 1-naphthyl2-naphthylMiscellaneous
Cyclophane baseY is any one in N, O, S, R3, R4, R5, R6, R7, R8, R9, R10, R11, R12, R13, R14,
R15, R16, R17, R18, R19, R20, R21, R22, R23, R24Optionally from H, halogen, C1-C16Alkyl, C1-C16Oxyl, hydrocarbon sulfur
Base, amino, amido, thiophene, any one in pyrroles, X is F, Cl, Br, I, OAc, CF3SO3In any one.
The method of synthesis alkenyl silanes compounds the most according to claim 1, is characterized in that, its structure of described silane
Formula isWherein R30, R31, R32It is optionally hydrogen, alkyl, alkoxyl, substituted aryl, substituted heteroaryl.
The method of synthesis alkenyl silanes compounds the most according to claim 1 and 2, is characterized in that, described CoX2-OIP
The structural formula of complex is optically pure following compound or its enantiomer or raceme, R25, R26, R27, R28, R29Optionally from C1-
C16Alkyl, naphthyl, substituted aryl, benzyl:
X is F, Cl, Br, I, OAc, CF3SO3In any one.
The method of synthesis alkenyl silanes compounds the most according to claim 1, is characterized in that having in described synthetic method
The participation of organic solvent, described organic solvent be benzene, carbon tetrachloride, toluene, oxolane, ether, dichloromethane, acetonitrile,
Dioxane, petroleum ether, hexamethylene, normal hexane, ethyl acetate, chloroform, N, any one in N-diformamide.
The method of synthesis alkenyl silanes compounds the most according to claim 1, is characterized in that, in described synthetic method not
Add any solvent.
6., according to the method for the synthesis alkenyl silanes compounds described in claim 1 or 2 or 4 or 5, it is characterized in that, described
Alkynes, silane, CoX2-OIP complex, the mol ratio of sodium triethylborohydride are 1:1:0.004-0.02:0.012-0.06.
7., according to the method for the synthesis alkenyl silanes compounds described in claim 1 or 2 or 4 or 5, it is characterized in that, described conjunction
In one-tenth method, reaction temperature is-10 DEG C～40 DEG C.
The method of synthesis alkenyl silanes compounds the most according to claim 7, is characterized in that, in described synthetic method,
Reaction temperature is 20 DEG C, and the response time is 5 minutes or 20 minutes.
9., according to the method for the synthesis alkenyl silanes compounds described in claim 1 or 2 or 3 or 4 or 5 or 8, it is characterized in that,
The product of gained is to be separated form through recrystallization, thin layer chromatography, column chromatography or decompression distillation.
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| CN110028504A (en) * | 2018-01-12 | 2019-07-19 | 南开大学 | The preparation method and applications of phenanthroline and its cobalt complex that 2,9- diaryl replaces |
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Cited By (3)
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| CN110028504A (en) * | 2018-01-12 | 2019-07-19 | 南开大学 | The preparation method and applications of phenanthroline and its cobalt complex that 2,9- diaryl replaces |
| CN110028504B (en) * | 2018-01-12 | 2023-01-13 | 南开大学 | Preparation method and application of 2, 9-diaryl substituted o-phenanthroline and cobalt complex thereof |
| CN109111333A (en) * | 2018-06-26 | 2019-01-01 | 浙江大学 | It is a kind of chiral together with two silicon substrate alkane compounds and its synthetic method and application |
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