CN107226823A - A kind of preparation method of hexa-atomic two silicon dioxane compound - Google Patents
A kind of preparation method of hexa-atomic two silicon dioxane compound Download PDFInfo
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- -1 silicon dioxane compound Chemical class 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000012429 reaction media Substances 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 74
- 229910052757 nitrogen Inorganic materials 0.000 claims description 37
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 22
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000003446 ligand Substances 0.000 claims description 15
- 239000010948 rhodium Substances 0.000 claims description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 11
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 7
- 150000003624 transition metals Chemical class 0.000 claims description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 229910052741 iridium Inorganic materials 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical group [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004950 trifluoroalkyl group Chemical group 0.000 claims description 4
- 238000011065 in-situ storage Methods 0.000 claims description 3
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 23
- 230000015572 biosynthetic process Effects 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 120
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- 239000000203 mixture Substances 0.000 description 21
- 150000002118 epoxides Chemical class 0.000 description 17
- 238000004440 column chromatography Methods 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 15
- JVVRCYWZTJLJSG-UHFFFAOYSA-N 4-dimethylaminophenol Chemical compound CN(C)C1=CC=C(O)C=C1 JVVRCYWZTJLJSG-UHFFFAOYSA-N 0.000 description 15
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 15
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-dimethylaminopyridine Substances CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 15
- 238000001035 drying Methods 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 15
- 150000002460 imidazoles Chemical class 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 239000012074 organic phase Substances 0.000 description 15
- 239000003208 petroleum Substances 0.000 description 15
- 238000010898 silica gel chromatography Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 10
- 229910000144 sodium(I) superoxide Inorganic materials 0.000 description 8
- NMNGQZMSFBMYLV-UHFFFAOYSA-N hydroxy-di(propan-2-yl)silane Chemical compound CC(C)[SiH](O)C(C)C NMNGQZMSFBMYLV-UHFFFAOYSA-N 0.000 description 7
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 6
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 6
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- BPMGYFSWCJZSBA-UHFFFAOYSA-N C[SiH](C)O[SiH3] Chemical compound C[SiH](C)O[SiH3] BPMGYFSWCJZSBA-UHFFFAOYSA-N 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- ZGPFIXGIGHQFMD-UHFFFAOYSA-N C(C)(C)[SiH](O[SiH](C)C)C(C)C Chemical compound C(C)(C)[SiH](O[SiH](C)C)C(C)C ZGPFIXGIGHQFMD-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000002639 sodium chloride Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- 238000006037 Brook Silaketone rearrangement reaction Methods 0.000 description 1
- MFUNORLMTGMIEL-UHFFFAOYSA-N C[SiH](Cl)C.[N] Chemical compound C[SiH](Cl)C.[N] MFUNORLMTGMIEL-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- RQMJBTDULKHSNC-UHFFFAOYSA-N O1[SiH2]O[SiH2]C=C1 Chemical compound O1[SiH2]O[SiH2]C=C1 RQMJBTDULKHSNC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- OSVXSBDYLRYLIG-UHFFFAOYSA-N chlorine dioxide Inorganic materials O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
Abstract
Field is synthesized the present invention relates to organosilicon; to solve hexa-atomic two silicon dioxane compound problem present in synthesis; the present invention proposes a kind of preparation method of hexa-atomic two silicon dioxane compound; using dialkyl group disiloxane of the structural formula as shown in (I) as raw material; with catalyst precarsor, hydrogen acceptor, in reaction medium; product is isolated after 3 24h in being reacted at 90 120 DEG C under inert gas shielding, i.e., a kind of hexa-atomic two silicon dioxane compound.This method is respectively provided with well adapting to property to the substrate containing diverse location and property substituent, preferably can obtain the hexa-atomic two silicon dioxane compound of series by yield.
Description
Technical field
Field is synthesized the present invention relates to organosilicon, and in particular to one kind is silated using transition metal-catalyzed intramolecular dehydrogenation
The preparation method of the hexa-atomic silaoxacyclen of reaction synthesis.
Background technology
Organo-silicon compound are widely used, can be applicable to the fields such as medicine, material, Synthetic Organic Chemistry, hexa-atomic two silicon two
Oxygen helerocyclics is widely used as organic synthesis intermediate.Phenolic compound is present in many natural products, more attaches most importance to
What is wanted is that phenol segment portion is often the key structure that such compound plays its bioactivity especially pharmaceutical activity, therefore,
The feature phenolic compound that complexity is constructed by simple phenol is always one of problem of organic chemist's concern.Organosilicon
Carbon-silicon key in compound can carry out conversion by series reaction is used to synthesizing other important compounds, such as halogenation, oxidation and
Coupling reaction etc..In addition, adjacent hydroxyaryl silicon compound can as aryne precursor synthesizing other aromatic compounds, or
For catalyzed coupling reaction.
Generally, the formation of phenolic hydroxyl group ortho position carbon-silicon key can be realized by following approach：(1) ortho selectivity is carried out successively
Bromination, O- is silated, Retro-Brook reactions；(2) the adjacent halogenated phenols of the hydroxyl protection of metal catalytic is silated；(3) phenol is determined
To ortho-metalated/silated etc..These methods more or less have that such as organo-lithium compound is to some functions
Group's poor compatibility, reaction selectivity is poor, and environment is unfriendly etc., thus how to develop some efficient reactions for constructing carbon-silicon key
The organo-silicon compound with significant application value can also be formed while above mentioned problem is overcome turns into chemical work at this stage
One of direction that person makes great efforts.
In numerous carbon-silicon key formation reaction, the directly silated strategy of carbon-hydrogen link has unrivaled advantage：Should
Method had both avoided the advance functionalization of initiation material, had good functional group's compatibility toward contact.The direct silicon substrate of carbon-hydrogen link
Change the selective problems for reacting that the ultimate challenge faced is such reaction.Because carbon-hydrogen link has very high bond energy, relatively surely
Fixed, priming reaction condition is harsh, frequently results in emulative carbon-hydrogen link activation and occurs, so as to trigger side reaction.Although existing text
The direct silated reaction between report aryl alkyl ethers compound and silane molecule is offered, but the reaction is to aryl substrate substituent
Steric hindrance is sensitive, and to use excessive silated reagent, and reaction substrate scope and Atom economy need further raising
(Oyamada, J.；Nishiura, M.；Hou, Z.Angew.Chem., Int.Ed.2011,50,10720-10723.).
The content of the invention
To solve hexa-atomic two silicon dioxane compound problem present in synthesis, the present invention proposes one kind hexa-atomic two
The preparation method of silicon dioxane compound, this method is respectively provided with preferably to the substrate containing diverse location and property substituent
Adaptability, preferably can obtain the hexa-atomic two silicon dioxane compound of series by yield.
The present invention is achieved by the following technical solutions：A kind of preparation method of hexa-atomic two silicon dioxane compound,
Using dialkyl group disiloxane of the structural formula as shown in (I) as raw material, with catalyst precarsor, hydrogen acceptor is lazy in reaction medium
Property gas shield under isolate product after 3-24h is reacted at 90-120 DEG C, i.e. the hexa-atomic two silicon dioxane compound of one kind.Make
To be preferred, product is separated using conventional separation methods.
Structure formula (I) is as follows：
In formula：R1Selected from alkyl, alkoxy, aryl, carbonyl, halogen, a kind of, R in trifluoroalkyl2And R3Independently select
From methyl, ethyl, propyl group is a kind of in phenyl.
Reaction structure formula is：
The structural formula of described hexa-atomic two silicon dioxane compound is such as shown in (II)：
In formula：R1Selected from alkyl, alkoxy, aryl, carbonyl, halogen, a kind of, R in trifluoroalkyl2And R3Independently select
From methyl, ethyl, propyl group is a kind of in phenyl.
Preferably, the molar concentration of dialkyl group disiloxane of the structural formula as shown in (I) is 0.2-2.0mol/L.As
It is preferred that, dialkyl group disiloxane of the structural formula as shown in (I) uses popular response side by corresponding phenol epoxide silanol and chlorosilane
It is prepared by method；
Preferably, described catalyst precarsor is the network that transition metal precursors are formed in situ with nitrogen ligand or Phosphine ligands
Compound, transition metal precursors consumption is the 0.5~2% of dialkyl group disiloxane mole of the structural formula as shown in (I), nitrogen ligand
Or 0.5~5% that the consumption of Phosphine ligands is dialkyl group disiloxane mole of the structural formula as shown in (I).
Described transition metal precursors are selected from rhodium, iridium complex or rhodium, iridium metals salt, and rhodium, iridium metals salt are preferably
RhCl(PPh3)3, [Rh (cod) Cl]2, [Rh (nbd) Cl]2, [Rh (coe)2Cl]2, [Ir (cod) Cl]2, [Ir (cod) OMe]2In
It is a kind of.
Nitrogen ligand is selected from 2, a kind of in 2 '-bipyridyl, 1,10- Phens and its derivative, Phosphine ligands be selected from single phosphine or
Diphosphine compound.Preferably, the one kind of the nitrogen ligand, Phosphine ligands in following structural formula：
Preferably, hydrogen acceptor is selected from a kind of in ENB, cyclohexene, 3,3- dimethyl -1- butylene, hydrogen acceptor
Consumption be dialkyl group disiloxane mole of the structural formula as shown in (I) 110-300%.
Preferably, reaction medium is a kind of in tetrahydrofuran, dioxane, toluene, dimethylbenzene.Usage amount is anti-to make
Answer the amount that thing fully reacts.
Dialkyl group disiloxane of the invention using easily prepared structural formula as shown in (I) utilizes transition metal as raw material
The intramolecular dehydrogenation of catalysis is silated to react the synthesis for realizing hexa-atomic two silicon dioxane compound.
Compared with prior art, the beneficial effects of the invention are as follows：Catalyzed precursor is commercial reagents or is formed in situ, and is operated
Simply.Reaction can be completed in certain temperature stirring, crude product is concentrated under reduced pressure after rapid column chromatography removal of impurities can obtain sterling, after
Processing is convenient.And product can be used as exceedingly useful organic synthesis intermediate.
Embodiment
The present invention is described in further detail below by embodiment, raw materials used commercially available in embodiment or use
It is prepared by conventional method.
Dialkyl group disiloxane reactant is prepared using following conventional method in embodiment：
Preparation example 1: 1, the synthesis of 1- diisopropyls -1- (p-methylphenyl epoxide) -3,3- dimethyldisiloxanes
Diisopropyl (to toloxyl) silanol (10mmol, 2.4g), imidazoles are added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.81 (d, J=8.3Hz, 2H), 6.60 (d, J=8.4Hz, 1H), 4.68-4.54
(m, 1H), 2.07 (s, 3H), 0.84 (s, 14H), 0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 152.1,129.7,129.0,118.9,19.8,16.2 (2), 12.2,0.0.
The synthesis of preparation example 2: 1- (4- (tert-butyl group) phenoxy group) -1,1- diisopropyl -3,3- dimethyldisiloxanes
(4- (tert-butyl group) phenoxy group) diisopropyl silanol (10mmol, 2.8g), imidazoles is added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.06-7.01 (m, 2H), 6.68-6.60 (m, 2H), 4.69-4.55 (m, 1H),
(dd, J=5.9,2.6Hz, the 6H) of 1.10 (s, 9H), 0.85 (m, 14H), 0.00
13C NMR (101MHz, CDCl3) δ 151.9,143.2,125.3,118.5,33.4,30.8,16.3 (2), 12.2,
0.0.
Preparation example 3：The conjunction of 1- ([1,1 '-biphenyl] -4- bases epoxide) -1,1- diisopropyl -3,3- dimethyldisiloxanes
Into
([1,1 '-biphenyl] -4- bases epoxide) diisopropyl silanol (10mmol, 3.0g) is added into 100mL round-bottomed flasks,
Imidazoles (15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under gas shielded and obtains white opacity solution.It is stirred at room temperature complete to reaction.
Mixture is washed through saturated sodium-chloride water solution, organic phase anhydrous sodium sulfate drying, and mixture is through silica gel column chromatography, petroleum ether
Elution, drains to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.36 (dt, J=3.0,1.7Hz, 2H), 7.32-7.24 (m, 2H), 7.21 (dd,
J=10.4,4.9Hz, 2H), 7.15-7.06 (m, 1H), 6.86-6.74 (m, 2H), 4.68-4.60 (m, 1H), 0.94-0.83
(m, 15H), 0.02 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 154.0,140.2,133.6,127.9,127.2,125.9,125.8,119.4,
16.2 (2), 12.2, -0.0.
Preparation example 4：The synthesis of 1- (4- fluorophenoxies) -1,1- diisopropyl -3,3- dimethyldisiloxanes
(4- fluorophenoxies) diisopropyl silanol (10mmol, 2.4g), imidazoles are added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.76-6.61 (m, 4H), 4.64-4.56 (m, 1H), 0.85 (m, 14H), -0.00
(d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 156.94 (d, J=238.6Hz), 150.42 (d, J=2.4Hz), 119.99
(d, J=8.0Hz), 114.90 (d, J=22.9Hz), 16.2,16.2,12.2, -0.0.
Preparation example 5：The synthesis of 1- (4- chlorophenoxies) -1,1- diisopropyl -3,3- dimethyldisiloxanes
(4- chlorophenoxies) diisopropyl silanol (10mmol, 2.6g), imidazoles are added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.01-6.94 (m, 2H), 6.67-6.60 (m, 2H), 4.62-4.57 (m, 1H),
0.84 (m, 14H), -0.00 (d, J=2.7Hz, 6H)
13C NMR (101MHz, CDCl3) δ 153.1,128.5,125.0,120.4,16.2 (2), 12.2,0.0.
Preparation example 6：The synthesis of 1- (2- ethyls phenoxy group) -1,1- diisopropyl -3,3- dimethyldisiloxanes
(2- ethyls phenoxy group) diisopropyl silanol (10mmol, 2.5g), imidazoles is added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.22-7.14 (m, 1H), 7.12-7.05 (m, 1H), 6.97-6.89 (m, 2H),
4.90-4.85 (m, 1H), 2.68 (q, J=7.5Hz, 2H), 1.24 (t, J=7.5Hz, 3H), 1.18-1.05 (m, 14H), 0.26
(d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 152.3,133.5,128.4,125.7,120.4,117.7,22.8,16.4,
16.3,13.5,12.4,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C16H30NaO2Si2：333.1677, Found：
333.1685.
Preparation example 7：The synthesis of 1- (2- (tert-butyl group) phenoxy group) -1,1- diisopropyl -3,3- dimethyldisiloxanes
(2- (tert-butyl group) phenoxy group) diisopropyl silanol (10mmol, 2.8g), imidazoles is added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.21-7.05 (m, 1H), 6.91-6.79 (m, 1H), 6.77-6.57 (m, 2H),
(d, J=2.8Hz, the 6H) of 4.72-4.62 (m, 1H), 1.20 (s, 9H), 0.94-0.83 (m, 14H), 0.05
13C NMR (101MHz, CDCl3) δ 153.4,138.0,126.2,125.9,119.8,118.4,33.9,28.9,
16.5,16.4,12.5, -0.0.
Preparation example 8: 1, the synthesis of 1- diisopropyl -3,3- dimethyl -1- (a tolyl epoxide) disiloxane
Diisopropyl (a tolyl epoxide) silanol (10mmol, 2.4g), imidazoles is added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.90 (t, J=7.7Hz, 1H), 6.60-6.48 (m, 3H), 4.65-4.56 (m,
1H), (d, J=2.8Hz, the 6H) of 2.10 (s, 3H), 0.85 (m, 14H), -0.00
13C NMR (101MHz, CDCl3) δ 154.3,138.5,128.2,121.4,119.9,116.1,20.6,16.3
(2), 12.2, -0.0.
HRMS(APCI)：m/z：[M+Na]+calculated for C18H28NaO2Si2：355.1520, Found：
355.1538.
Preparation example 9：The synthesis of 1- (2,4- dimethyl phenoxy) -1,1- diisopropyl -3,3- dimethyldisiloxanes
(2,4- dimethyl phenoxy) diisopropyl silanol (10mmol, 2.5g), imidazoles are added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.97 (m, 1H), 6.88 (dd, J=8.1,1.9Hz, 1H), 6.81 (d, J=
8.1Hz, 1H), 5.00-4.78 (m, 1H), 2.29 (s, 3H), 2.24 (s, 3H), 1.12-1.07 (m, 14H), 0.26 (d, J=
2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 150.5,130.7,129.4,127.2,126.1,117.5,19.8,16.4,
16.3,15.9,12.4,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C16H30NaO2Si2：333.1677, Found：
333.1684.
Preparation example 10：
The synthesis of 1,1- diisopropyl -1- ((5,6,7,8- naphthane -1- bases) epoxide) -3,3- dimethyldisiloxanes
Into 100mL round-bottomed flasks add diisopropyl ((5,6,7,8- naphthane -1- bases) epoxide) silanol (10mmol,
2.8g), imidazoles (15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to
0 DEG C, dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under nitrogen protection and obtains white opacity solution.It is stirred at room temperature to reaction
Completely.Mixture is washed through saturated sodium-chloride water solution, organic phase anhydrous sodium sulfate drying, mixture through silica gel column chromatography,
Petroleum ether is eluted, and drains to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.98 (t, J=7.8Hz, 1H), 6.73 (t, J=7.2Hz, 2H), 4.90-4.84
(m, 1H), 2.78 (t, J=5.9Hz, 2H), 2.70 (t, J=6.1Hz, 2H), 1.87-1.73 (m, 4H), 1.12-1.07 (m,
14H), 0.26 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 152.3,138.0,127.1,124.6,121.1,114.5,28.9,23.1,
22.2 (2), 16.4,16.3,12.4,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C18H32NaO2Si2：359.1833, Found：
359.1844.
Preparation example 11：The synthesis of 1,1- diisopropyl -1- (1- naphthyls epoxide) -3,3- dimethyldisiloxanes
Diisopropyl (1- naphthyls epoxide) silanol (10mmol, 2.7g), imidazoles is added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 8.20-8.11 (m, 1H), 7.79-7.69 (m, 1H), 7.48-7.33 (m, 3H),
7.24 (t, J=7.9Hz, 1H), 6.92 (dd, J=7.5,0.8Hz, 1H), 4.90-4.74 (m, 1H), 1.09-0.98 (m,
14H), 0.15 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 150.4,134.2,126.8 (2), 125.3,125.1,124.3,121.8,
120.3,111.9,16.4 (2), 12.4,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C18H28NaO2Si2：355.1520, Found：
355.1532.
Preparation example 12: 1, the synthesis of 1- diisopropyls -1- (2- naphthyls epoxide) -3,3- dimethyldisiloxanes
Diisopropyl (2- naphthyls epoxide) silanol (10mmol, 2.7g), imidazoles is added into 100mL round-bottomed flasks
(15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, nitrogen is protected
Dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under shield and obtains white opacity solution.It is stirred at room temperature complete to reaction.Mixing
Thing is washed through saturated sodium-chloride water solution, and organic phase anhydrous sodium sulfate drying, mixture is washed through silica gel column chromatography, petroleum ether
It is de-, drain to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.74-7.51 (m, 3H), 7.36-7.26 (m, 1H), 7.26-7.13 (m, 2H),
7.03 (dd, J=8.8,2.4Hz, 1H), 4.74 (dq, J=5.5,2.7Hz, 1H), 1.08-0.92 (m, 14H), 0.11 (d, J=
2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 152.2,133.8,128.5,128.4,126.8,125.9,125.3,122.9,
121.0,113.9,16.3,16.2,12.2,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C18H28NaO2Si2：355.1520, Found：
355.1538.
Preparation example 13：
(8R, 9S, 13S, 14S) -3- ((1,1- diisopropyl -3,3- dimethyldisiloxane base) epoxide) -13- methyl -
The synthesis of 6,7,8,9,11,12,13,14,15,16- decahydro -17H- cyclopentas [a] phenanthrene -17- ketone
Into 100mL round-bottomed flasks add (8R, 9S, 13S, 14S) -3- ((hydroxyl diisopropylsilyl) epoxide) -
13- methyl -6,7,8,9,11,12,13,14,15,16- decahydro -17H- cyclopentas [a] phenanthrene -17- ketone (10mmol,
4.0g), imidazoles (15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to
0 DEG C, dimethylchlorosilane (11mmol, 1.2mL) is added dropwise under nitrogen protection and obtains white opacity solution.It is stirred at room temperature to reaction
Completely.Mixture is washed through saturated sodium-chloride water solution, organic phase anhydrous sodium sulfate drying, mixture through silica gel column chromatography,
Petroleum ether is eluted, and drains to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.90 (d, J=8.4Hz, 1H), 6.56-6.39 (m, 2H), 4.67- 4.54 (m,
1H), 2.72-2.57 (m, 2H), 2.28 (dd, J=18.8,8.5Hz, 1H), 2.16 (dd, J=9.8,4.2Hz, 1H), 2.09-
(d, J=2.8Hz, the 6H) of 1.66 (m, 5H), 1.48-1.14 (m, 6H), 0.88-0.78 (m, 14H), 0.70 (s, 3H), -0.00
13C NMR (101MHz, CDCl3) δ 220.1,152.2,136.6,131.7,125.3,118.9,116.4,49.7,
47.2,43.3,37.6,35.1,30.8,28.7,25.8,25.1,20.8,16.3,16.2,13.1,12.1,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C26H42NaO3Si2：481.2565, Found：
481.2555.
Preparation example 14：
1- ((2 '-(benzyloxy)-[1,1 '-dinaphthalene] -2- bases) epoxide)-silica of 1,1- diisopropyls -3,3- dimethyl two
The synthesis of alkane
((2 '-(benzyloxy)-[1,1 '-dinaphthalene] -2- bases) epoxide) diisopropyl silanol is added into 100mL round-bottomed flasks
(10mmol, 5.1g), imidazoles (15mmol, 1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride
20mL, is cooled to 0 DEG C, and dimethylchlorosilane (11mmol, 1.2mL), which is added dropwise, under nitrogen protection obtains white opacity solution.Room
Temperature stirring is complete to reaction.Mixture is washed through saturated sodium-chloride water solution, organic phase anhydrous sodium sulfate drying, mixture warp
Silica gel column chromatography, petroleum ether elution, drains to obtain colourless liquid.
1H NMR (400MHz, CDCl3) δ 13.01-12.96 (m, 1H), 7.69 (ddd, J=25.4,13.1,6.7Hz,
4H), 7.31-6.94 (m, 11H), 6.93-6.81 (m, 2H), 4.89 (s, 2H), 4.67-4.54 (m, 1H), 0.63-0.52 (m,
4H), 0.51-0.35 (m, 10H), 0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 153.4,149.9,137.0,133.8,133.5,128.8,128.6,128.3,
128.1,127.4,127.4,127.1,126.9,126.5,125.9,125.8,125.3 (2), 125.1,124.9,120.3
(2), 119.9,114.9,70.3,16.0,15.8 (2), 12.3,12.1,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C35H40NaO3Si2：587.2408, Found：
587.2418.
Preparation example 15: the synthesis of Isosorbide-5-Nitrae-bis- ((1,1- diisopropyl -3,3- dimethyldisiloxane base) epoxide) benzene
Added into 100mL round-bottomed flasks (Isosorbide-5-Nitrae-phenylene double (epoxide)) double (diisopropylsilyl alcohol) (10mmol,
3.7g), imidazoles (30mmol, 2.04g), DMAP (2mmol, 24.4mg), dry methylene chloride 40mL is cooled to
0 DEG C, dimethylchlorosilane (22mmol, 2.4mL) is added dropwise under nitrogen protection and obtains white opacity solution.It is stirred at room temperature to reaction
Completely.Mixture is washed through saturated sodium-chloride water solution, organic phase anhydrous sodium sulfate drying, mixture through silica gel column chromatography,
Petroleum ether is eluted, and drains to obtain colourless liquid.
1H NMR (400MHz, CDCl3) (s, the 12H) of δ 6.58 (s, 4H), 4.61 (s, 2H), 0.85 (s, 29H), 0.0013C NMR (101MHz, CDCl3) δ 148.6,119.6,16.2 (2), 12.1,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C22H46NaO4Si4：509.2365, Found：
509.2385.
Embodiment 1：Synthesize 2,2-diisopropyl-4,4,6-trimethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
1,1- diisopropyls -1- (p-methylphenyl epoxide) -3,3- prepared by preparation example 1 is added into Shlenk bottles of 25mL
Dimethyldisiloxane (1mmol, 296.5mg), [Ir (cod) Cl]2(0.01mmol, 6.7mg), 1,10-phen
(0.02mmol, 3.6mg), ENB (1.2mmol, 113mg) adds tetrahydrofuran 2mL, is stirred at room temperature under nitrogen protection
5 minutes, stirred 12 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 241mg, yield is 82%.
1H NMR (400MHz, CDCl3) δ 6.99 (dd, J=8.2,1.9Hz, 1H), 6.94-6.85 (m, 1H), 6.75-
(s, the 6H) of 6.64 (m, 1H), 2.18 (s, 3H), 0.94 (m, 14H), 0.30
13C NMR (101MHz, CDCl3) δ 157.9,132.3,130.9,128.5,123.1,117.5,19.3,15.3
(2), 11.5,0.0.
HRMS(APCI)：m/z：[M+H]+calculated for C15H27O2Si2：295.1544, Found：
295.1541.
Embodiment 2：
Synthesize 6- (tert-butyl) -2,2-diisopropyl-4,4-dimethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
Added into Shlenk bottles of 25mL 1- (4- (tert-butyl group) phenoxy group)-1,1- diisopropyls prepared by preparation example 2-
3,3- dimethyldisiloxanes (1mmol, 338.6mg), [Ir (cod) Cl]2(0.005mmol, 3.4mg), 3,4,7,8-Me4-
Phen (0.01mmol, 2.4mg), ENB (1.1mmol, 103.6mg) adds tetrahydrofuran 1mL, room under nitrogen protection
Temperature stirring 5 minutes, is stirred 24 hours in 80 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 188mg, yield is 56%.
1H NMR (400MHz, CDCl3) δ 7.24 (dd, J=8.6,2.6Hz, 1H), 7.09 (d, J=2.6Hz, 1H), 6.74
(d, J=8.6Hz, 1H), 1.24 (s, 9H), 1.00-0.95 (m, 14H), 0.34 (s, 6H)
13C NMR (101MHz, CDCl3) δ 157.7,141.7,128.2,127.2,122.3,116.9,32.7,30.2,
15.2 (2), 11.4,0.0.
Embodiment 3：
Synthesize 2,2-diisopropyl-4,4-dimethyl-6-phenyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
1- ([1,1 '-biphenyl] -4- bases epoxide) -1,1- diisopropyls prepared by preparation example 3 are added into Shlenk bottles of 25mL
Base -3,3- dimethyldisiloxane (1mmol, 358.2mg), [Ir (cod) OMe]2(0.005mmol, 3.3mg), 3,4,7,8-
Me4- phen (0.01mmol, 2.4mg), cyclohexene (1.5mmol, 123.2mg) adds dioxane 4mL under nitrogen protection,
It is stirred at room temperature 5 minutes, is stirred 20 hours in 90 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 220mg, yield is 62%.
1H NMR (400MHz, CDCl3) δ 7.47-7.36 (m, 3H), 7.34-7.24 (m, 3H), 7.22-7.14 (m, 1H),
(s, the 6H) of 6.84 (t, J=9.8Hz, 1H), 0.97-0.91 (m, 14H), 0.32
13C NMR (101MHz, CDCl3) δ 159.7,139.7,132.5,130.7,129.0,127.3,125.4,125.3,
123.6,118.0,15.2 (2), 11.47,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C20H28NaO2Si2：379.1520, Found：
379.1530.
Embodiment 4：
Synthesize 6-fluoro-2,2-diisopropyl-4,4-dimethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
1- (4- fluorophenoxies) -1,1- diisopropyls -3,3- bis- prepared by preparation example 4 are added into Shlenk bottles of 25mL
Tetramethyldisiloxane (1mmol, 300.5mg), [Rh (cod) C1]2(0.02mmol, 9.9mg), dppp (0.04mmol,
16.5mg), 3,3- dimethyl -1- butylene (2mmol, 168.3mg), adds dioxane 0.5mL under nitrogen protection, and room temperature is stirred
Mix 5 minutes, stirred 2 hours in 110 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 248mg, yield is 83%.
1H NMR (400MHz, CDCl3) δ 6.91-6.83 (m, 1H), 6.75 (ddd, J=13.2,8.4,3.7Hz, 2H),
0.95 (m, 14H), 0.31 (s, 6H)
13C NMR (101MHz, CDCl3) δ 156.22 (d, J=240.8Hz), 156.12 (d, J=1.8Hz), 125.19
(d, J=3.9Hz), 119.20 (d, J=7.0Hz), 117.54 (d, J=20.5Hz), 116.99 (d, J=23.1Hz), 15.5
(2), 11.7,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C14H24FNaO2Si2：299.1293, Found：
299.1293.
Embodiment 5：
Synthesize 6-chloro-2,2-diisopropyl-4,4-dimethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
1- (4- chlorophenoxies) -1,1- diisopropyls -3,3- bis- prepared by preparation example 5 are added into Shlenk bottles of 25mL
Tetramethyldisiloxane (1mmol, 317mg), [Rh (coe)2Cl]2(0.015mmol, 10.8mg), three (4- anisyls) phosphines
(0.03mmol, 10.6mg), 3,3- dimethyl -1- butylene (3.0mmol, 252.5mg), adds dimethylbenzene under nitrogen protection
3mL, is stirred at room temperature 5 minutes, is stirred 10 hours in 120 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains white solid 239mg, yield
For 76%
1H NMR (400MHz, CDCl3) δ 7.12 (dd, J=8.7,2.7Hz, 1H), 7.02 (d, J=2.7Hz, 1H), 6.71
(d, J=8.7Hz, 1H), 0.97-0.91 (m, 14H), 0.31 (s, 6H)
13C NMR (101MHz, CDCl3) δ 158.8,131.5,130.2,125.8,124.8,119.5,15.4 (2),
11.6.0.0.
HRMS(ESI)：m/z：[M+H]+calculated for C14H24ClO2Si2：315.0998, Found：
315.0988.
Embodiment 6：
Synthesize 8-ethyl-2,2-diisopropyl-4,4-dimethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
1- (2- ethyls phenoxy group) -1,1- diisopropyls -3,3- prepared by preparation example 6 are added into Shlenk bottles of 25mL
The synthesis (1mmol, 310.6mg) of dimethyldisiloxane, [Rh (coe)2Cl]2(0.015mmol, 10.8mg), three (4- methoxies
Phenyl) phosphine (0.03mmol, 10.6mg), 3,3- dimethyl -1- butylene (3.0mmol, 252.5mg) add under nitrogen protection
Dimethylbenzene 3mL, is stirred at room temperature 5 minutes, is stirred 10 hours in 120 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 253mg, is produced
Rate is 82%
1H NMR (400MHz, CDCl3) δ 7.07 (dd, J=7.4,1.7Hz, 1H), 6.93 (dd, J=7.2,1.8Hz,
1H), 6.78 (t, J=7.3Hz, 1H), 2.59-2.47 (m, 2H), 1.10 (t, J=7.5Hz, 3H), 0.94 (m, 14H), 0.27
(s, 6H)
13C NMR (101MHz, CDCl3) δ 157.6,131.8,129.6,129.5,122.5,119.4,22.2,15.2
(2), 12.7,11.5,0.0.
Embodiment 7：
Synthesize 8- (tert-butyl) -2,2-diisopropyl-4,4-dimethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
Added into Shlenk bottles of 25mL 1- (2- (tert-butyl group) phenoxy group)-1,1- diisopropyls prepared by preparation example 7-
3,3- dimethyldisiloxanes (1mmol, 338.6mg), [Rh (nbd) Cl]2(0.02mmol, 9.2mg), 4,4 '-tBu2-
Bipyridine (0.05mmol, 13.4mg), ENB (2.2mmol, 207mg), adds toluene under nitrogen protection
1.5mL, is stirred at room temperature 5 minutes, is stirred 8 hours in 110 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 209mg, yield is
62%.
1H NMR (400MHz, CDCl3) δ 7.19 (dd, J=7.7,1.7Hz, 1H), 6.91 (dd, J=7.1,1.7Hz,
1H), (s, the 6H) of 6.76 (t, J=7.4Hz, 1H), 1.26 (s, 9H), 0.98-0.85 (m, 14H), 0.25
13C NMR (101MHz, CDCl3) δ 158.5,136.7,129.9,127.4,123.3,119.1,33.4,28.3,
14.9,14.8,11.2,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C18H32NaO2Si2：359.1833, Found：
359.1845.
Embodiment 8：Synthesize 2,2-diisopropyl-4,4,7-trimethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
1,1- diisopropyl -3,3- dimethyl -1- (tolyl prepared by preparation example 8 is added into Shlenk bottles of 25mL
Epoxide) disiloxane (1mmol, 296.5mg), [Rh (nbd) Cl]2(0.02mmol, 9.2mg), 4,4 '-tBu2-bipyridine
(0.05mmol, 13.4mg), ENB (2.2mmol, 207mg) adds toluene 1.5mL, is stirred at room temperature 5 under nitrogen protection
Minute, stirred 8 hours in 110 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains white solid 165mg, yield is 56%
1H NMR (400MHz, CDCl3) δ 6.99 (d, J=7.4Hz, 1H), 6.69 (d, J=7.4Hz, 1H), 6.62 (s,
1H), 2.21 (s, 3H), 1.03-0.90 (m, 14H), 0.32-0.26 (m, 6H)
13C NMR (101MHz, CDCl3) δ 160.1,140.5,131.9,120.5,119.8,118.3,20.0,15.2,
11.4.0.0.
HRMS(APCI)：m/z：[M+H]+calculated for C15H27O2Si2：295.1544, Found：
295.1546.
Embodiment 9：
Synthesize 2,2-diisopropyl-4,4,6,8-tetramethyl-4H-benzo [e] [1,3,2,4]
dioxadisiline
1- (2,4- dimethyl phenoxy) -1,1- diisopropyls-prepared by preparation example 9 are added into Shlenk bottles of 25mL
3,3- dimethyldisiloxanes (1mmol, 310.6mg), [Ir (cod) OMe]2(0.005mmol, 3.3mg), 3,4,7,8-Me4-
Phen (0.01mmol, 2.4mg), cyclohexene (1.5mmol, 123.2mg) adds dioxane 4mL, room temperature under nitrogen protection
Stirring 5 minutes, is stirred 20 hours in 90 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 167mg, yield is 54%.
1H NMR (400MHz, CDCl3) δ 6.89 (d, J=1.3Hz, 1H), 6.73 (d, J=1.7Hz, 1H), 2.15 (s,
3H), (s, the 6H) of 2.09 (s, 3H), 0.96-0.91 (m, 14H), 0.28
13C NMR (101MHz, CDCl3) δ 155.8,132.1,129.6,128.2,125.7,122.2,19.2,15.3
(2), 14.9,11.5, -0.0.
HRMS(ESI)：m/z：[M+H]+calculated for C16H29O2Si2：309.1701, Found：309.1696.
Embodiment 10：
Synthesize 2,2-diisopropyl-4,4-dimethyl-7,8,9,10-tetrahydro-4H-naphtho [2,1-
E] [1,3,2,4] dioxadisiline
1,1- diisopropyls -1- ((5,6,7,8- naphthane -1- prepared by preparation example 10 are added into Shlenk bottles of 25mL
Base) epoxide) -3,3- dimethyldisiloxanes (1mmol, 336.6mg), [Ir (cod) C1]2(0.01mmol, 6.7mg), 3,4,
7,8-Me4- phen (0.02mmol, 4.8mg), ENB (1.2mmol, 113mg), adds tetrahydrofuran under nitrogen protection
2mL, is stirred at room temperature 5 minutes, is stirred 24 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 291mg, yield is
87%.
1H NMR (400MHz, CDCl3) δ 6.82 (d, J=7.5Hz, 1H), 6.59 (d, J=7.5Hz, 1H), 2.62 (t, J
=6.0Hz, 2H), 2.54 (t, J=6.1Hz, 2H), 1.78-1.55 (m, 4H), 0.95-0.89 (m, 14H), 0.25 (s, 6H)
13C NMR (101MHz, CDCl3) δ 157.7,139.6,128.3,125.6,120.3,118.7,28.5,21.9,
21.6,21.4,15.2 (2), 11.5,0.0.
Embodiment 11：
Synthesize 2,2-diisopropyl-4,4-dimethyl-4H-naphtho [2,1-e] [1,3,2,4]
dioxadisiline
1,1- diisopropyls -1- (1- naphthyls epoxide) -3,3- bis- prepared by preparation example 11 is added into Shlenk bottles of 25mL
Tetramethyldisiloxane (1mmol, 332.6mg), [Ir (cod) Cl]2(0.01mmol, 6.7mg), 3,4,7,8-Me4-phen
(0.02mmol, 4.8mg), ENB (1.2mmol, 113mg) adds tetrahydrofuran 2mL, is stirred at room temperature under nitrogen protection
5 minutes, stirred 24 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 278mg, yield is 84%.
1H NMR (400MHz, CDCl3) δ 8.14-8.05 (m, 1H), 7.60 (dt, J=4.1,2.6Hz, 1H), 7.39-
(s, the 6H) of 7.23 (m, 3H), 7.13-7.03 (m, 1H), 0.93 (dt, J=17.7,5.7Hz, 14H), 0.28
13C NMR (101MHz, CDCl3) δ 156.6,134.7,127.7,126.2,125.7,125.3,124.1,121.4,
119.2,115.9,15.4 (2), 11.7,0.0.
Embodiment 12：
Synthesize 2,2-diisopropyl-4,4-dimethyl-4H-naphtho [2,3-e] [1,3,2,4]
dioxadisiline
1,1- diisopropyls -1- (2- naphthyls epoxide) -3,3- prepared by preparation example 12 is added into Shlenk bottles of 25mL
Dimethyldisiloxane (1mmol, 332.6mg), [Ir (cod) Cl]2(0.01 mmol, 6.7mg), 3,4,7,8-Me4-phen
(0.02mmol, 4.8mg), ENB (1.2mmol, 113mg) adds tetrahydrofuran 2mL, is stirred at room temperature under nitrogen protection
5 minutes, stirred 24 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 273mg, yield is 82%.
1H NMR (400MHz, CDCl3) δ 7.61 (dd, J=28.0,7.4Hz, 3H), 7.31 (ddd, J=8.2,6.9,
1.2Hz, 1H), 7.20 (ddd, J=8.0,6.9,1.1Hz, 1H), 7.16 (s, 1H), 1.02-0.91 (m, 14H), 0.38 (s,
6H).
13C NMR (101MHz, CDCl3) δ 156.7,134.5,133.2,127.4,126.5,126.2,125.2,125.0,
122.1,111.9,15.1 (2), 11.3,0.0.
HRMS(APCI)：m/z：[M+H]+calculated for C18H27O2Si2：331.1544, Found：
331.1559.
Embodiment 13：
Synthesis (3aS, 3bR, 11bS, 13aS) -8,8-diisopropyl-10,10,13a-trimethyl-3,3a, 3b,
4,5,10,11b, 12,13,13a-decahydrocyclopenta [7,8] phenanthro [3,2-e] [1,3,2,4]
dioxadisilin-1(2H)-one
Added into Shlenk bottles of 25mL (8R, 9S, 13S, 14S) -3- prepared by preparation example 13 ((1,1- diisopropyl -
3,3- dimethyldisiloxane bases) epoxide) -13- methyl -6,7,8,9,11,12,13,14,15,16- decahydro -17H- rings penta 2
Alkene simultaneously [a] phenanthrene -17- ketone (1mmol, 458.7mg), [Ir (cod) Cl]2(0.01 mmol, 6.7mg), 3,4,7,8-Me4-phen
(0.02mmol, 4.8mg), ENB (1.2mmol, 113mg) adds tetrahydrofuran 2mL, is stirred at room temperature under nitrogen protection
5 minutes, stirred 24 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 365mg, yield is 80%.
1H NMR (400MHz, CDCl3) δ 6.94 (s, 1H), 6.50 (s, 1H), 2.84-2.65 (m, 2H), 2.38 (dd, J=
18.8,8.5Hz, 1H), 2.32-2.24 (m, 1H), 2.18-2.08 (m, 1H), 2.08-1.77 (m, 4H), 1.54-1.31 (m,
6H), (d, J=2.5Hz, the 6H) of 0.95-0.86 (m, 14H), 0.79 (s, 3H), 0.24
13C NMR (101MHz, CDCl3) δ 219.5,157.9,138.9,130.7,128.6,120.2,117.4,52.0,
49.1,46.6,42.6,36.9,34.5,30.2,28.1,25.1,24.5,20.2,15.2 (2), 12.5,11.5,11.3,0.2,
0.0.
Embodiment 14：
Synthesize 10- (2- (benzyloxy) naphthalen-1-yl) -2,2-diisopropyl-4,4-dimethyl-
4H-naphtho [2,3-e] [1,3,2,4] dioxadisiline
1- ((2 '-(benzyloxy)-[1,1 '-dinaphthalene] -2- bases) prepared by preparation example 14 is added into Shlenk bottles of 25mL
Epoxide) -1,1- diisopropyls -3,3- dimethyldisiloxane (1mmol, 564.8mg), [Ir (cod) Cl]2(0.01mmol,
6.7mg), 3,4,7,8-Me4- phen (0.02mmol, 4.8mg), ENB (1.2mmol, 113mg), under nitrogen protection
Tetrahydrofuran 2mL is added, is stirred at room temperature 5 minutes, is stirred 24 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product
456mg, yield is 81%.
1H NMR (400MHz, CDCl3) δ 7.95-7.64 (m, 4H), 7.31 (d, J=9.0Hz, 1H), 7.27-6.82 (m,
11H), 4.97 (s, 2H), 0.76-0.35 (m, 20H)
13C NMR (101MHz, CDCl3) δ 155.3,154.2,137.9,135.6,134.7,134.2,129.4,128.9
(2), 128.1,128.0,127.7,127.3,127.2,126.7,126.5,125.9 (2), 125.5,123.5,123.3,
121.2,119.6,115.7,71.1,16.3,16.2,15.9,12.5,1.9,1.6,1.1.
HRMS(ESI)：m/z：[M+Na]+calculated for C35H38NaO3Si2：585.2252, Found：
585.2267.
Embodiment 15：
Synthesis 2,2,7,7-tetraisopropyl-4,4,9,9-tetramethyl-4,9-dihydrobenzo [1,2-
e：4,5-e '] bis ([1,3,2,4] dioxadisiline)
Isosorbide-5-Nitrae-bis- ((1,1- diisopropyl -3,3- dimethyl two prepared by preparation example 15 are added into Shlenk bottles of 25mL
Siloxy group) epoxide) benzene (1mmol, 484.9mg), [Ir (cod) Cl]2(0.02mmol, 13.4mg), 3,4,7,8-Me4-phen
(0.04mmol, 9.6mg), ENB (2.4mmol, 226mg) adds tetrahydrofuran 4mL, is stirred at room temperature under nitrogen protection
5 minutes, stirred 24 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 377mg, yield is 78%.
1H NMR (400MHz, CDCl3) (s, the 12H) of δ 6.70 (s, 2H), 1.13-0.98 (m, 29H), 0.40
13C NMR (101MHz, CDCl3) δ 153.6,127.2,121.5,15.5 (2), 11.7,0.0.
HRMS(ESI)：m/z：[M+Na]+calculated for C22H42NaO4Si4：505.2052, Found：
505.2059。
Claims (9)
1. a kind of preparation method of hexa-atomic two silicon dioxane compound, it is characterised in that with dioxane of the structural formula as shown in (I)
Base disiloxane is reactant, and catalyst precarsor, hydrogen acceptor, in reaction medium, in 90- under inert gas shielding
Product is isolated after reacting 3-24h at 120 DEG C, hexa-atomic two silicon dioxane compound is obtained, structure formula (I) is as follows：
In formula：R1Selected from alkyl, alkoxy, aryl, carbonyl, halogen, a kind of, R in trifluoroalkyl2And R3It is respectively and independently selected from first
It is a kind of in base, ethyl, propyl group, phenyl.
2. the preparation method of a kind of hexa-atomic two silicon dioxane compound according to claim 1, it is characterised in that described
Hexa-atomic two silicon dioxane compound structural formula such as shown in (II)：
In formula：R1Selected from alkyl, alkoxy, aryl, carbonyl, halogen, a kind of, R in trifluoroalkyl2And R3It is respectively and independently selected from first
It is a kind of in base, ethyl, propyl group, phenyl.
3. a kind of preparation method of hexa-atomic two silicon dioxane compound according to claim 1, it is characterised in that structure
The molar concentration of dialkyl group disiloxane of the formula as shown in (I) is 0.2-2.0mol/L.
4. a kind of preparation method of hexa-atomic two silicon dioxane compound according to claim 1, it is characterised in that catalysis
Agent precursor is selected from the complex compound that transition metal precursors are formed in situ with nitrogen ligand or Phosphine ligands, and transition metal precursors consumption is structure
The consumption of the 0.5~2% of dialkyl group disiloxane mole of the formula as shown in (I), nitrogen ligand or Phosphine ligands is structural formula such as (I)
The 0.5~5% of shown dialkyl group disiloxane mole.
5. a kind of preparation method of hexa-atomic two silicon dioxane compound according to claim 4, it is characterised in that transition
Metal precursor is selected from rhodium, iridium complex or rhodium, iridium metals salt.
6. the preparation method of a kind of hexa-atomic two silicon dioxane compound according to claim 4, it is characterised in that nitrogen is matched somebody with somebody
Body is selected from one kind in 2,2 '-bipyridyl, 1,10- Phens and its derivative, and Phosphine ligands are selected from single phosphine or diphosphine compound.
7. the preparation method of a kind of hexa-atomic two silicon dioxane compound according to claim 6, it is characterised in that described
The one kind of nitrogen ligand, Phosphine ligands in following structural formula：
8. a kind of preparation method of hexa-atomic two silicon dioxane compound according to claim 1, it is characterised in that hydrogen
Acceptor is selected from one kind in ENB, cyclohexene, 3,3- dimethyl -1- butylene, and the consumption of hydrogen acceptor is structural formula such as (I) institute
The 110-300% for the dialkyl group disiloxane mole shown.
9. a kind of preparation method of hexa-atomic two silicon dioxane compound according to claim 1, it is characterised in that reaction
Medium is a kind of in tetrahydrofuran, dioxane, toluene, dimethylbenzene.
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| YAN LIN等: "Iridium-catalyzed intramolecular C-H silylation of siloxane-tethered arene and hydrosilane: facile and catalytic synthesis of cyclic siloxanes", 《ADVANCED SYNTHESIS & CATALYSIS》 * |
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