CN107226822A - A kind of preparation method of hexa-atomic silaoxacyclen - Google Patents
A kind of preparation method of hexa-atomic silaoxacyclen Download PDFInfo
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- CN107226822A CN107226822A CN201710247241.XA CN201710247241A CN107226822A CN 107226822 A CN107226822 A CN 107226822A CN 201710247241 A CN201710247241 A CN 201710247241A CN 107226822 A CN107226822 A CN 107226822A
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- silaoxacyclen
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- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical compound [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000012429 reaction media Substances 0.000 claims abstract description 5
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 70
- 229910052757 nitrogen Inorganic materials 0.000 claims description 35
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 24
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 20
- -1 siloxanes Chemical class 0.000 claims description 18
- 239000003446 ligand Substances 0.000 claims description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000010948 rhodium Substances 0.000 claims description 11
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 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
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- VURFVHCLMJOLKN-UHFFFAOYSA-N Diphosphine Natural products PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 125000004950 trifluoroalkyl group Chemical group 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
- 238000003786 synthesis reaction Methods 0.000 abstract description 37
- 230000015572 biosynthetic process Effects 0.000 abstract description 36
- 238000000034 method Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 3
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 118
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 45
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 30
- 238000005160 1H NMR spectroscopy Methods 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 28
- 239000000203 mixture Substances 0.000 description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 20
- 239000000047 product Substances 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 18
- 238000004440 column chromatography Methods 0.000 description 16
- JARCABNSJCAMPJ-UHFFFAOYSA-N 2H-oxadisiline Chemical compound O1[SiH2][SiH]=CC=C1 JARCABNSJCAMPJ-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
- 238000001035 drying Methods 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
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 14
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 13
- 150000002460 imidazoles Chemical class 0.000 description 13
- 238000002156 mixing Methods 0.000 description 7
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 7
- 235000002639 sodium chloride Nutrition 0.000 description 7
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 238000010828 elution Methods 0.000 description 6
- NMNGQZMSFBMYLV-UHFFFAOYSA-N hydroxy-di(propan-2-yl)silane Chemical compound CC(C)[SiH](O)C(C)C NMNGQZMSFBMYLV-UHFFFAOYSA-N 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 229910000077 silane Inorganic materials 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229960002668 sodium chloride Drugs 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 125000004343 1-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000006179 2-methyl benzyl group Chemical group [H]C1=C([H])C(=C(C([H])=C1[H])C([H])([H])*)C([H])([H])[H] 0.000 description 3
- 125000003852 3-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C(Cl)=C1[H])C([H])([H])* 0.000 description 3
- 125000006497 3-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C(OC([H])([H])[H])=C1[H])C([H])([H])* 0.000 description 3
- 125000006180 3-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C(=C1[H])C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000006283 4-chlorobenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1Cl)C([H])([H])* 0.000 description 3
- 125000004217 4-methoxybenzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1OC([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000006181 4-methyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])C([H])([H])* 0.000 description 3
- BPMGYFSWCJZSBA-UHFFFAOYSA-N C[SiH](C)O[SiH3] Chemical compound C[SiH](C)O[SiH3] BPMGYFSWCJZSBA-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 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
- 125000006491 4-t-butyl benzyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])*)C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- MFUNORLMTGMIEL-UHFFFAOYSA-N C[SiH](Cl)C.[N] Chemical compound C[SiH](Cl)C.[N] MFUNORLMTGMIEL-UHFFFAOYSA-N 0.000 description 2
- JVGNTAMBJZGKBT-UHFFFAOYSA-N O[SiH2]CC1=CC=CC=C1 Chemical compound O[SiH2]CC1=CC=CC=C1 JVGNTAMBJZGKBT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 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
- 238000005755 formation reaction Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 230000007704 transition 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
- KUKRLSJNTMLPPK-UHFFFAOYSA-N 4,7,7-trimethylbicyclo[2.2.1]hept-2-ene Chemical group C1CC2(C)C=CC1C2(C)C KUKRLSJNTMLPPK-UHFFFAOYSA-N 0.000 description 1
- GLVKGYRREXOCIB-UHFFFAOYSA-N Bornylene Natural products CC1CCC(C(C)(C)C)C=C1 GLVKGYRREXOCIB-UHFFFAOYSA-N 0.000 description 1
- 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 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002947 alkylene group Chemical group 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- IRYDWXGNXNZHLW-UHFFFAOYSA-N benzyl-hydroxy-di(propan-2-yl)silane Chemical compound CC(C)[Si](O)(C(C)C)CC1=CC=CC=C1 IRYDWXGNXNZHLW-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 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
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 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
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
- C07F7/0872—Preparation and treatment thereof
- C07F7/0889—Reactions not involving the Si atom of the Si-O-Si sequence
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- 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 silaoxacyclen problem present in synthesis; the present invention proposes a kind of preparation method of hexa-atomic silaoxacyclen; using dialkyl group disiloxane as raw material; with catalyst precarsor, hydrogen acceptor, in reaction medium; in being reacted at 90 120 DEG C after 3 24h with isolating product under inert gas shielding, i.e., hexa-atomic silaoxacyclen.This method is respectively provided with well adapting to property to the substrate containing diverse location and property substituent, preferably can obtain serial hexa-atomic silaoxacyclen 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 silica is miscellaneous
Cycle compound is widely used as organic synthesis intermediate, and the carbon in organo-silicon compound-silicon key can be entered by series reaction
Row conversion is used to synthesize other important compounds, such as halogenation, oxidation and coupling reaction etc..In addition, silicon-oxygen key also can be in specific examination
Agent effect is lower to carry out selective fracture.Therefore, the study on the synthesis of organo-silicon compound receives much attention always.Generally, carbon-silicon key
Formation can be anti-to the coupling of the substitution reaction of chlorine or hydrogen silane, halogenated aryl hydrocarbon and hydrogen silane or disilane by organometallic reagent
Should and hydrosilylation etc. realize.These methods more or less there are problems that, such as RMgBr, organo-lithium compound
To some functional group's poor compatibilities, reaction selectivity is poor, and environment is unfriendly etc., thus how to develop some it is efficient construct carbon-
The organo-silicon compound that the reaction of silicon key can also form high added value while above mentioned problem is overcome turn into chemical work at this stage
One of direction that author 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 the reaction.With intermolecular directly different, the intramolecular of silated reaction
Carbon-hydrogen link it is silated reaction also have the characteristics that：(1) it is prevented effectively from using excessive aryl compound or silane；(2)
By the way that the synthesis of bifunctional compound can be realized to the further derivative of product；(3) have for high enantioselective synthesis chirality
Organic silicon compound is provided may.But because carbon-hydrogen link has very high bond energy, stablize relatively, priming reaction condition is harsh, often
Often result in emulative carbon-hydrogen link activation to occur, so as to trigger side reaction.Although existing document report aryl compound and silane
Intermolecular directly silated reaction, but most of aryl substrates are confined to hetero-aromatic ring, the aromatic ring containing big steric hindrance or directing group.
At the same time it was noticed that benzyl silanol can be used for the reaction such as carbon-hydrogen link alkylene, oxidation of palladium chtalyst as directing group.But
There is not document report also using silanol as the directing group of silated reaction.Due in silanol hydroxyl can for association hydrogen silane,
Possibility is provided for the silated reaction of intramolecular.As far as we know, it be yet there are no in addition to the hetero atoms such as nitrogen, oxygen by other miscellaneous
Atom is used for the report of the reaction.
The content of the invention
To solve hexa-atomic silaoxacyclen problem present in synthesis, it is miscellaneous that the present invention proposes a kind of hexa-atomic silica
The preparation method of cycle compound, this method is respectively provided with well adapting to property to the substrate containing diverse location and property substituent,
Preferably serial hexa-atomic silaoxacyclen can be obtained by yield.
The present invention is achieved by the following technical solutions：A kind of preparation method of hexa-atomic silaoxacyclen, with two
Alkyl disiloxane is raw material, with catalyst precarsor, hydrogen acceptor, in reaction medium, in 90-120 under inert gas shielding
Product is isolated after reacting 3-24h at DEG C, i.e., hexa-atomic silaoxacyclen.Preferably, being separated using conventional separation methods
Product.
Reaction structure formula is：
The structural formula of described hexa-atomic silaoxacyclen is such as shown in (I)：
In formula, R1Selected from alkyl, alkoxy, aryl, halogen, a kind of, R in trifluoroalkyl2、R3、R4It is respectively and independently selected from alkane
Base or aryl.
Preferably, the molar concentration of dialkyl group disiloxane is 0.2-2.0mol/L.Preferably, the silica of dialkyl group two
Alkane is prepared by corresponding benzyl silanol and chlorosilane using popular response；
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, and nitrogenous or Phosphine ligands consumptions are two
The 0.5~5% of alkyl disiloxane mole.
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.The one kind of the nitrogen ligand, Phosphine ligands in structural formula is such as shown in (II)：
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 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.
The present invention realizes hexa-atomic silaoxacyclen using the transition metal-catalyzed silated reaction of intramolecular dehydrogenation
Synthesis, using easily prepared dialkyl group disiloxane as raw material, the silated reaction of dehydrogenation through intramolecular, which can be efficiently synthesized, is
Arrange hexa-atomic silaoxacyclen.
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 is prepared using following conventional method in embodiment：
Preparation example 1：The synthesis of 1- benzyl -1,1- diisopropyl -3,3- dimethyldisiloxanes
The addition benzyl diisopropyl silanol (10mmol, 2.2g) into 100mL round-bottomed flasks, imidazoles (15mmol,
1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL, are cooled to 0 DEG C, under nitrogen protection dropwise
Add dimethylchlorosilane (11mmol, 1.2mL) and obtain white opacity solution.It is stirred at room temperature complete to reaction.Mixture is through saturation
Sodium-chloride water solution is washed, organic phase anhydrous sodium sulfate drying, and mixture is drained through silica gel column chromatography, petroleum ether elution
Colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.12-7.03 (m, 2H), 6.94 (dd, J=15.9,7.4Hz, 3H), 4.61
(dq, J=5.5,2.7Hz, 1H), 2.03 (s, 2H), 0.90-0.79 (m, 14H), -0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 138.7,127.8,127.2,123.1,21.1,16.4 (2), 12.2,0.0.
Preparation example 2：The synthesis of 1,1- diisopropyl -1- (4- methyl-benzyls) -3,3- dimethyldisiloxanes
Diisopropyl (4- methyl-benzyls) 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 6.86 (q, J=8.2Hz, 4H), 4.61 (dq, J=5.5,2.7Hz, 1H), 2.15
(s, 3H), 1.98 (s, 2H), 0.85-0.80 (m, 14H), -0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 135.3,132.3,127.8,127.6,20.4,19.9,16.4 (2), 12.1,
0.0.
Preparation example 3：The synthesis of 1- (4- t-butylbenzyls) -1,1- diisopropyl -3,3- dimethyldisiloxanes
(4- t-butylbenzyls) diisopropyl silanol (10mmol, 2.8g), 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 7.15-7.10 (m, 2H), 6.92 (d, J=8.3Hz, 2H), 4.63 (dq, J=
5.4,2.7Hz, 1H), 2.03 (s, 2H), 1.21 (s, 9H), 0.91-0.85 (m, 14H), -0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 145.9,135.3,127.4,124.0,33.3,30.5,20.2,16.4 (2),
12.2, -0.0.
Preparation example 4：The synthesis of 1,1- diisopropyl -1- (4- methoxy-benzyls) -3,3- dimethyldisiloxanes
(4- methoxy-benzyls) 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 6.85 (t, J=5.7Hz, 2H), 6.67-6.59 (m, 2H), 4.60 (dq, J=
5.5,2.7Hz, 1H), 3.63 (s, 3H), 1.94 (s, 2H), 0.85-0.78 (m, 14H), -0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 155.7,130.4,128.4,112.7,54.3,19.6,16.3 (2), 12.0,
0.0.
Preparation example 5：The synthesis of 1- (4- luorobenzyls) -1,1- diisopropyl -3,3- dimethyldisiloxanes
Addition (4- luorobenzyls) diisopropyl silanol (10mmol, 2.4g) into 100mL round-bottomed flasks, imidazoles (15mmol,
1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL, are cooled to 0 DEG C, under nitrogen protection dropwise
Add dimethylchlorosilane (11mmol, 1.2mL) and obtain white opacity solution.It is stirred at room temperature complete to reaction.Mixture is through saturation
Sodium-chloride water solution is washed, organic phase anhydrous sodium sulfate drying, and mixture is drained through silica gel column chromatography, petroleum ether elution
Colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.93-6.86 (m, 2H), 6.76 (ddd, J=8.7,5.8,2.5Hz, 2H),
(d, J=2.8Hz, the 6H) of 4.60 (dq, J=5.5,2.7Hz, 1H), 1.98 (s, 2H), 0.87-0.79 (m, 14H), -0.00
13C NMR (101MHz, CDCl3) δ 159.5 (d, J=241.5Hz), 134.2 (d, J=3.0Hz), 128.8 (d, J
=7.4Hz), 113.9 (d, J=21.0Hz), 20.0,16.3 (2), 12.1, -0.0.
Preparation example 6：The synthesis of 1- (4- chlorobenzyls) -1,1- diisopropyl -3,3- dimethyldisiloxanes
Addition (4- chlorobenzyls) diisopropyl silanol (10mmol, 2.6g) into 100mL round-bottomed flasks, imidazoles (15mmol,
1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL, are cooled to 0 DEG C, under nitrogen protection dropwise
Add dimethylchlorosilane (11mmol, 1.2mL) and obtain white opacity solution.It is stirred at room temperature complete to reaction.Mixture is through saturation
Sodium-chloride water solution is washed, organic phase anhydrous sodium sulfate drying, and mixture is drained through silica gel column chromatography, petroleum ether elution
Colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.03 (d, J=8.4Hz, 2H), 6.87 (d, J=8.3Hz, 2H), 4.59 (dq, J
=5.5,2.7Hz, 1H), 1.98 (s, 2H), 0.86-0.78 (m, 14H), -0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 137.3,128.9,128.7,127.2,20.5,16.3 (2), 12.1, -0.0.
Preparation example 7：The synthesis of 1,1- diisopropyl -1- (3- methyl-benzyls) -3,3- dimethyldisiloxanes
Diisopropyl (3- methyl-benzyls) 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 6.97 (t, J=7.5Hz, 1H), 6.83-6.70 (m, 3H), 4.61 (m, 1H),
(d, J=2.8Hz, the 6H) of 2.17 (s, 3H), 1.99 (s, 2H), 0.89-0.77 (m, 14H), -0.00
13C NMR (101MHz, CDCl3) δ 138.6,136.6,128.7,127.1,124.8,123.8,20.9,20.5,
16.4 (2), 12.1,0.0.
Preparation example 8：The synthesis of 1- (3- chlorobenzyls) -1,1- diisopropyl -3,3- dimethyldisiloxanes
Addition (3- chlorobenzyls) diisopropyl silanol (10mmol, 2.6g) into 100mL round-bottomed flasks, imidazoles (15mmol,
1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL, are cooled to 0 DEG C, under nitrogen protection dropwise
Add dimethylchlorosilane (11mmol, 1.2mL) and obtain white opacity solution.It is stirred at room temperature complete to reaction.Mixture is through saturation
Sodium-chloride water solution is washed, organic phase anhydrous sodium sulfate drying, and mixture is drained through silica gel column chromatography, petroleum ether elution
Colourless liquid.
1H NMR (400MHz, CDCl3) δ 6.94 (ddd, J=17.6,11.7,4.4Hz, 3H), 6.82 (d, J=7.5Hz,
1H), (d, J=2.8Hz, the 6H) of 4.67-4.55 (m, 1H), 1.99 (s, 2H), 0.86-0.80 (m, 14H), -0.00
13C NMR (101MHz, CDCl3) δ 141.1,133.0,128.4,127.8,125.9,123.3,20.9,16.4
(2), 12.2,0.0.
Preparation example 9：The synthesis of 1,1- diisopropyl -1- (3- methoxy-benzyls) -3,3- dimethyldisiloxanes
Diisopropyl (3- methoxy-benzyls) 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 6.98 (t, J=7.8Hz, 1H), 6.51 (ddd, J=11.7,10.6,5.1Hz,
3H), 4.61 (dq, J=5.5,2.7Hz, 1H), 3.64 (s, 3H), 2.01 (s, 2H), 0.89-0.77 (m, 14H), -0.00 (d, J
=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 158.6,140.3,128.0,120.4,113.5,108.5,54.1,21.2,
16.3 (2), 12.1,0.0.
Preparation example 10：The synthesis of 1,1- diisopropyl -1- (2- methyl-benzyls) -3,3- dimethyldisiloxanes
Diisopropyl (2- methyl-benzyls) 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 7.05-6.95 (m, 3H), 6.95-6.89 (m, 1H), 4.61 (dq, J=5.5,
2.8Hz, 1H), 2.22 (s, 3H), 2.09 (s, 2H), 0.95-0.89 (m, 14H), 0.00 (d, J=3.1Hz, 6H)
13C NMR (101MHz, CDCl3) δ 137.5,134.3,129.2,128.3,124.8,123.4,19.8,18.0,
16.6,16.5,12.8,0.0.
Preparation example 11：The synthesis of 1- ([1,1 '-biphenyl] -2- methyl) -1,1- diisopropyl -3,3- dimethyldisiloxanes
([1,1 '-biphenyl] -2- methyl) diisopropyl silanol (10mmol, 3.0g), miaow is added into 100mL round-bottomed flasks
Azoles (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 protection and obtains white opacity solution.It is stirred at room temperature complete to reaction.It is mixed
Compound 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 7.33-7.20 (m, 5H), 7.15 (ddd, J=8.4,7.1,1.7Hz, 2H),
(7.09 t, J=4.1Hz, 1H), 7.08-7.02 (m, 1H), 4.60 (dq, J=5.5,2.8Hz, 1H), 2.17 (s, 2H), 0.73-
0.67 (m, 14H), 0.02--0.02 (m, 6H)
13C NMR (101MHz, CDCl3) δ 141.6,140.2,136.3,129.4,129.0,128.9,127.2,126.1,
125.7,123.3,17.6,16.3,16.2,12.5, -0.0.
Preparation example 12：The synthesis of 1,1- diisopropyl -1- (1- phenylethyls) -3,3- dimethyldisiloxanes
Diisopropyl (1- phenylethyls) 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 7.09-7.00 (m, 2H), 7.00-6.86 (m, 3H), 4.62 (hept, J=
2.7Hz, 1H), 2.20 (q, J=7.6Hz, 1H), 1.22 (d, J=7.6Hz, 3H), 0.89-0.77 (m, 7H), 0.75-0.60
(m, 7H), 0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 144.6,127.0,126.7,123.4,26.6,16.8 (2), 16.5 (2),
14.8,11.8,11.7,0.0.
Preparation example 13：The synthesis of 1- benzhydryl -1,1- diisopropyl -3,3- dimethyldisiloxanes
The addition benzhydryl diisopropyl silanol (10mmol, 3.0g) into 100mL round-bottomed flasks, imidazoles (15mmol,
1.02g), DMAP (1mmol, 12.2mg), dry methylene chloride 20mL, are cooled to 0 DEG C, under nitrogen protection dropwise
Add dimethylchlorosilane (11mmol, 1.2mL) and obtain white opacity solution.It is stirred at room temperature complete to reaction.Mixture is through saturation
Sodium-chloride water solution is washed, organic phase anhydrous sodium sulfate drying, and mixture is drained through silica gel column chromatography, petroleum ether elution
Colourless liquid.
1H NMR (400MHz, CDCl3) δ 7.28 (dd, J=5.1,3.3Hz, 4H), 7.21-7.12 (m, 4H), 7.08-
7.00 (m, 2H), 4.78 (dq, J=5.5,2.8Hz, 1H), 3.54 (s, 1H), 0.90-0.74 (m, 14H), 0.13 (d, J=
2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 141.7,128.2,127.3,124.3,42.2,16.8,16.7,12.7,0.0.
Preparation example 14：The synthesis of 1,1- diisopropyl -1- (1- menaphthyls) -3,3- dimethyldisiloxanes is justified to 100mL
Diisopropyl (1- menaphthyls) silanol (10mmol, 2.7g), imidazoles (15mmol, 1.02g), 4- dimethylaminos are added in the flask of bottom
Pyridine (1mmol, 12.2mg), dry methylene chloride 20mL is cooled to 0 DEG C, dimethylchlorosilane is added dropwise under nitrogen protection
(11mmol, 1.2mL) 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, mixture drains to obtain colourless liquid through silica gel column chromatography, petroleum ether elution.
1H NMR (400MHz, CDCl3) δ 8.17-8.10 (m, 1H), 7.93-7.88 (m, 1H), 7.70 (d, J=8.1Hz,
1H), 7.59-7.50 (m, 2H), 7.47-7.40 (m, 1H), 7.38-7.30 (m, 1H), 4.65 (m, 1H), 2.71 (s, 2H),
1.10-1.03 (m, 15H), 0.00 (d, J=2.8Hz, 6H)
13C NMR (101MHz, CDCl3) δ 136.0,133.3,131.5,127.9,125.2,124.8,124.6,124.5,
124.4,124.1,18.1,16.8,16.7,12.8,0.0.
Preparation example 15：The synthesis of Isosorbide-5-Nitrae-bis- ((1,1- diisopropyl -3,3- dimethyldisiloxane base) methyl) benzene to
(Isosorbide-5-Nitrae-phenylene is double (methylene)) double (diisopropylsilyl alcohol) (10mmol, 3.7g), miaow are added in 100mL round-bottomed flasks
Azoles (30mmol, 2.04g), DMAP (2mmol, 24.4mg), dry methylene chloride 40mL is cooled to 0 DEG C, nitrogen
Dimethylchlorosilane (22mmol, 2.4mL) is added dropwise under protection and obtains white opacity solution.It is stirred at room temperature complete to reaction.It is mixed
Compound 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 6.78 (s, 4H), 4.62-4.57 (m, 2H), 1.93 (s, 4H), 0.83-0.73
(m, 28H), -0.00 (d, J=2.8Hz, 12H)
13C NMR (101MHz, CDCl3) δ 133.8,127.5,20.3,16.3,12.0,0.0.
Embodiment 1：
Synthesize 3,3-diisopropyl-1,1-dimethyl-3,4-dihydro-1H-benzo [c] [1,2,6]
oxadisiline
The silicon of 1- benzyl -1,1- diisopropyls -3,3- dimethyl two prepared by preparation example 1 is added into Shlenk bottles of 25mL
Oxygen alkane (1mmol, 280.5mg), [Ir (cod) Cl]2(0.01mmol, 6.7mg), 1,10-phen (0.02mmol, 3.6mg), drop
Bornylene (1.2mmol, 113mg), adds tetrahydrofuran 2mL, is stirred at room temperature 5 minutes under nitrogen protection, and 12 are stirred in 100 DEG C
Hour.It is concentrated under reduced pressure after rapid column chromatography, obtains product 222mg, yield is 80%.
1H NMR (400MHz, CDCl3) δ 7.36-7.27 (m, 1H), 7.27-7.18 (m, 1H), 7.16-7.06 (m, 2H),
(s, the 6H) of 2.14 (s, 2H), 0.90 (d, J=2.7Hz, 14H), 0.34
13C NMR (101MHz, CDCl3) δ 144.3,136.7,132.0,129.3,128.8,123.4,17.8,16.5,
16.3,12.2,0.0.
HRMS(APCI)：m/z：[M+H]+calculated for C15H27OSi2：279.1595, Found：279.1590.
Embodiment 2：
Synthesis 3,3-diisopropyl-1,1,7-trimethyl-3,4-dihydro-1H-benzo [c] [1,2,6]
oxadisiline
1,1- diisopropyls -1- (4- methyl-benzyls) -3,3- bis- prepared by preparation example 2 is added into Shlenk bottles of 25mL
Tetramethyldisiloxane (1mmol, 294.6mg), [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 under nitrogen protection, and room temperature is stirred
Mix 5 minutes, stirred 24 hours in 80 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 152mg, yield is 52%.
1H NMR (400MHz, CDCl3) δ 7.05 (s, 1H), 6.97 (dq, J=16.6,4.7Hz, 2H), 2.23 (s, 3H),
(s, the 6H) of 2.04 (s, 2H), 0.85 (m, 14H), 0.28
13C NMR (101MHz, CDCl3) δ 140.9,136.5,132.7,132.5,129.6,129.3,20.1,16.9,
16.3,16.3,12.2,0.0.
Embodiment 3：
Synthesize 7- (tert-butyl) -3,3-diisopropyl-1,1-dimethyl-3,4-dihydro-1H-benzo
[c] [1,2,6] oxadisiline
1- (4- (tert-butyl group) benzyl) -1,1- diisopropyl -3 prepared by preparation example 3 are added into Shlenk bottles of 25mL,
3- dimethyldisiloxanes (1mmol, 336.7mg), [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 201mg, yield is 60%.
1H NMR (400MHz, CDCl3) δ 7.40-7.26 (m, 2H), 7.08 (d, J=8.0Hz, 1H), 2.15 (s, 2H),
(s, the 6H) of 1.33 (s, 9H), 0.98-0.93 (m, 14H), 0.39
13C NMR (101MHz, CDCl3) δ 145.7,140.8,135.9,128.9,128.5,125.7,33.3,30.5,
16.8,16.4,16.2,12.1,0.0.
Embodiment 4：
Synthesis 3,3-diisopropyl-7-methoxy-1,1-dimethyl-3,4-dihydro-1H-benzo [c] [1,
2,6] oxadisiline
1,1- diisopropyls -1- (4- methoxy-benzyls) -3,3- prepared by preparation example 4 is added into Shlenk bottles of 25mL
Dimethyldisiloxane (1mmol, 312.6mg), [Rh (cod) Cl]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 251mg, yield is 81%.
1H NMR (400MHz, CDCl3) δ 6.97 (d, J=8.3Hz, 1H), 6.80 (d, J=2.9Hz, 1H), 6.72 (dd, J
=8.3,2.9Hz, 1H), 3.70 (s, 3H), 2.01 (s, 2H), 0.85 (m, 14H), 0.28 (s, 6H)
13C NMR (101MHz, CDCl3) δ 155.8,138.0,136.0,130.4,117.9,113.8,54.4,16.6,
16.4,16.3,12.3,0.0.
Embodiment 5：
Synthesis 7-fluoro-3,3-diisopropyl-1,1-dimethyl-3,4-dihydro-1H-benzo [c] [1,
2,6] oxadisiline
1- (4- luorobenzyls) -1,1- diisopropyl -3,3- diformazans prepared by preparation example 5 are added into Shlenk bottles of 25mL
Base disiloxane (1mmol, 298.5mg), [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, is stirred at room temperature under nitrogen protection
5 minutes, stirred 20 hours in 90 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 154mg, yield is 52%.
1H NMR (400MHz, CDCl3) δ 7.05 (dd, J=8.3,5.1Hz, 1H), 6.98 (dd, J=8.5,2.8Hz,
1H), (s, the 6H) of 6.94-6.84 (m, 1H), 2.09 (s, 2H), 0.89 (m, 14H), 0.33
13C NMR (101MHz, CDCl3) δ 159.94 (d, J=245.2Hz), 139.83 (d, J=3.2Hz), 139.27
(d, J=3.5Hz), 130.96 (d, J=6.4Hz), 118.39 (d, J=18.4Hz), 115.68 (d, J=20.9Hz), 16.9,
16.7,16.5,12.4,0.0.
Embodiment 6：
Synthesis 7-chloro-3,3-diisopropyl-1,1-dimethyl-3,4-dihydro-1H-benzo [c] [1,
2,6] oxadisiline
1- (4- chlorobenzyls) -1,1- diisopropyl -3,3- diformazans prepared by preparation example 6 are added into Shlenk bottles of 25mL
The synthesis (1mmol, 315mg) of base disiloxane, [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 product 250mg, yield is
80%
1H NMR (400MHz, CDCl3) δ 7.05 (d, J=2.4Hz, 1H), 6.99 (dd, J=8.1,2.4Hz, 1H), 6.84
(d, J=8.1Hz, 1H), 1.90 (s, 2H), 0.75-0.67 (m, 14H), 0.15 (s, 6H)
13C NMR (101MHz, CDCl3) δ 142.8,139.3,131.8,130.9,129.9,128.9,17.3,16.7,
16.5,12.3,0.0.
Embodiment 7：
Synthesis 3,3-diisopropyl-1,1,6-trimethyl-3,4-dihydro-1H-benzo [c] [1,2,6]
oxadisiline
1,1- diisopropyls -1- (3- methyl-benzyls) -3,3- bis- prepared by preparation example 7 is added into Shlenk bottles of 25mL
Tetramethyldisiloxane (1mmol, 294.6mg), [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 product 176mg, yield is 60%.
1H NMR (400MHz, CDCl3) δ 7.24-7.17 (m, 1H), 6.94 (d, J=6.3Hz, 2H), 2.28 (s, 3H),
(s, the 6H) of 2.10 (s, 2H), 0.91 (m, 14H), 0.32
13C NMR (101MHz, CDCl3) δ 144.2,138.6,133.1,132.0,130.1,124.2,20.5,17.5,
16.4,16.2,12.1,0.0.
Embodiment 8：
Synthesis 6-chloro-3,3-diisopropyl-1,1-dimethyl-3,4-dihydro-1H-benzo [c] [1,
2,6] oxadisiline
1- (3- chlorobenzyls) -1,1- diisopropyl -3,3- diformazans prepared by preparation example 8 are added into Shlenk bottles of 25mL
Base disiloxane (1mmol, 315.0mg), [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 281mg, yield is 90%.
1H NMR (400MHz, CDCl3) δ 7.18 (d, J=7.6Hz, 1H), 7.12-7.00 (m, 2H), 2.07 (s, 2H),
0.91-0.82 (m, 14H), 0.29 (s, 6H)
13C NMR (101MHz, CDCl3) δ 146.6,135.1,134.7,133.4,129.1,123.7,17.9,16.5,
16.3,12.2,0.0.
Embodiment 9：
Synthesis 3,3-diisopropyl-6-methoxy-1, l-dimethyl-3,4-dihydro-1H-benzo [c] [1,
2,6] oxadisiline
1,1- diisopropyls -1- (3- methoxy-benzyls) -3,3- prepared by preparation example 9 is added into Shlenk bottles of 25mL
Dimethyldisiloxane (1mmol, 308.6mg), [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 185mg, yield is 60%.
1H NMR (400MHz, CDCl3) δ 7.27-7.08 (m, 1H), 6.73-6.53 (m, 2H), 3.72 (s, 3H), 2.06
(s, 2H), 0.85 (m, 14H), 0.27 (d, J=3.3Hz, 6H)
13C NMR (101MHz, CDCl3) δ 159.8,146.2,133.3,127.9,115.0,108.6,53.9,18.0,
16.3,16.1,12.0,0.0.
Embodiment 10：
Synthesis 3,3-diisopropyl-1,1,5-trimethyl-3,4-dihydro-1H-benzo [c] [1,2,6]
oxadisiline
1,1- diisopropyls -1- (2- methyl-benzyls) -3,3- prepared by preparation example 10 is added into Shlenk bottles of 25mL
Dimethyldisiloxane (1mmol, 294.6mg), [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 240mg, yield is 82%.
1H NMR (400MHz, CDCl3) δ 7.24 (t, J=7.9Hz, 2H), 7.10 (t, J=7.3Hz, 1H), 2.39 (s,
3H), (s, the 6H) of 2.14 (s, 2H), 1.01-0.96 (m, 14H), 0.42
13C NMR (101MHz, CDCl3) δ 142.4,136.9,134.7,130.6,129.9,123.3,20.1,16.5,
16.3,12.6,12.1,0.0.
Embodiment 11：
Synthesis 3,3-diisopropyl-1,1-dimethyl-5-phenyl-3,4-dihydro-1H-benzo [c] [1,
2,6] oxadisiline
1- ([1,1 '-biphenyl] -2- methyl) -1,1- diisopropyls prepared by preparation example 11 are added into Shlenk bottles of 25mL
Base -3,3- dimethyldisiloxane (1mmol, 356.6mg), [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, room temperature under nitrogen protection
Stirring 5 minutes, is stirred 24 hours in 100 DEG C.It is concentrated under reduced pressure after rapid column chromatography, obtains product 273mg, yield is 77%.
1H NMR (400MHz, CDCl3) δ 7.45-7.30 (m, 6H), 7.27-7.19 (m, 2H), 2.10 (s, 2H), 0.93-
0.83 (m, 14H), 0.45 (s, 6H)
13C NMR (101MHz, CDCl3) δ 141.8,141.2,140.9,137.5,131.3,130.5,128.5,127.1,
125.7,123.1,16.3,16.1,14.5,11.9,0.0.
Embodiment 12：
Synthesis 3,3-diisopropyl-1, Isosorbide-5-Nitrae-trimethyl-3,4-dihydro-1H-benzo [c] [1,2,6]
oxadisiline
1,1- diisopropyls -1- (1- phenylethyls) -3,3- bis- prepared by preparation example 12 is added into Shlenk bottles of 25mL
Tetramethyldisiloxane (1mmol, 294.6mg), [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 155mg, yield is 53%.
1H NMR (400MHz, CDCl3) δ 7.24 (dd, J=12.3,4.5Hz, 2H), 7.13 (t, J=8.1Hz, 1H),
7.05 (t, J=7.3Hz, 1H), 2.36 (m, 1H), 1.31 (d, J=7.6Hz, 3H), 0.94-0.86 (m, 8H), 0.78 (m,
6H), 0.33 (s, 3H), 0.25 (s, 3H)
13C NMR (101MHz, CDCl3) δ 150.2,136.4,132.1,129.0,125.3,123.2,24.4,16.7,
16.6,16.5 (2), 14.3,11.8,11.6,0.5,0.0.
HRMS(APCI)：m/z：[M+H]+：293.1739.
Embodiment 13：
Synthesize 2,2-diisopropy1-4,4-dimethyl-1,4-dihydro-2H-naphtho [2,1-c] [1,2,6]
oxadisiline
1- benzhydryl -1,1- diisopropyl -3,3- dimethyl prepared by preparation example 13 is added into Shlenk bottles of 25mL
Disiloxane (1mmol, 330.6mg), [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 246mg, yield is 75%.
1H NMR (400MHz, CDCl3) δ 8.43 (d, J=8.5Hz, 1H), 8.03-7.99 (m, 1H), 7.85 (d, J=
8.1Hz, 1H), 7.70 (dddd, J=19.3,7.9,6.8,1.3Hz, 2H), 7.62 (d, J=8.1Hz, 1H), 2.74 (s, 2H),
1.18 1 1.12 (m, 14H), 0.63 (s, 6H)
13C NMR (101MHz, CDCl3) δ 141.3,133.8,133.6,131.6,128.1,127.9,125.0,124.9,
123.8,123.0,16.4,16.3,12.2,10.8,0.0.
Embodiment 14：
Synthesis 3,3-diisopropyl-1,1-dimethyl-4-phenyl-3,4-dihydro-1H-benzo [c] [1,
2,6] oxadisiline
1,1- diisopropyls -1- (1- menaphthyls) -3,3- diformazans prepared by preparation example 14 are added into Shlenk bottles of 25mL
Base disiloxane (1mmol, 356.6mg), [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 202mg, yield is 57%.
1H NMR (400MHz, CDCl3) δ 7.37-7.18 (m, 3H), 7.15-6.85 (m, 6H), 3.77 (s, 1H), 1.07-
(s, the 3H) of 0.79 (m, 8H), 0.68-0.54 (m, 6H), 0.43 (s, 3H), 0.33
13C NMR (101MHz, CDCl3) δ 147.8,140.2,136.3,132.2,129.1,127.8,127.2,124.6,
123.8,40.3,16.7,16.3 (2), 16.1,12.7,11.7,1.0,0.0.
Embodiment 15：
Synthesis 3,3,8,8-tetraisopropyl-1,1,6,6-tetramethyl-1,3,4,6,8,9-
Hexahydrobenzo [1,2-c：4,5-c '] bis ([1,2,6] oxadisiline)
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) methyl) benzene (1mmol, 481mg), [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 340mg, yield is 71%.
1H NMR (400MHz, CDCl3) δ 6.87 (s, 2H), 1.91 (s, 4H), 0.75-0.65 (m, 28H), 0.15 (s,
12H).
13C NMR (101MHz, CDC.
Claims (9)
1. a kind of preparation method of hexa-atomic silaoxacyclen, it is characterised in that using dialkyl group disiloxane as raw material, with urging
Agent precursor, hydrogen acceptor, in reaction medium, in being reacted at 90-120 DEG C after 3-24h with isolating under inert gas shielding
Product, i.e., hexa-atomic silaoxacyclen.
2. a kind of preparation method of hexa-atomic silaoxacyclen according to claim 1, it is characterised in that described six
The structural formula of first silaoxacyclen is such as shown in (I)：
In formula, R1Selected from alkyl, alkoxy, aryl, halogen, a kind of, R in trifluoroalkyl2、R3、R4Be respectively and independently selected from alkyl or
Aryl.
3. a kind of preparation method of hexa-atomic silaoxacyclen according to claim 1, it is characterised in that dialkyl group two
The molar concentration of siloxanes is 0.2-2.0mol/L.
4. the preparation method of a kind of hexa-atomic silaoxacyclen according to claim 1, it is characterised in that described urges
Agent precursor is the complex compound that transition metal precursors are formed in situ with nitrogen ligand or Phosphine ligands, and transition metal precursors consumption is two
The 0.5~2% of alkyl disiloxane mole, nitrogenous or Phosphine ligands consumptions for dialkyl group disiloxane mole 0.5~
5%.
5. a kind of preparation method of hexa-atomic silaoxacyclen 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 silaoxacyclen according to claim 4, it is characterised in that nitrogen ligand is selected
A kind of from 2,2 '-bipyridyl, 1,10- Phens and its derivative, Phosphine ligands are selected from single phosphine or diphosphine compound.
7. the preparation method of a kind of hexa-atomic silaoxacyclen according to claim 6, it is characterised in that the nitrogen is matched somebody with somebody
The one kind of body, Phosphine ligands in structural formula is such as shown in (II)：
8. a kind of preparation method of hexa-atomic silaoxacyclen according to claim 1, it is characterised in that hydrogen acceptor
A kind of in ENB, cyclohexene, 3,3- dimethyl -1- butylene, the consumption of hydrogen acceptor rubs for dialkyl group disiloxane
The 110-300% of your amount.
9. a kind of preparation method of hexa-atomic silaoxacyclen according to claim 1, it is characterised in that reaction medium
It is a kind of in tetrahydrofuran, dioxane, toluene, dimethylbenzene.
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| Title |
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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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| CN113072517A (en) * | 2021-04-07 | 2021-07-06 | 南京工业大学 | Synthetic method of five-membered oxygen heterocyclic compound |
| CN113072517B (en) * | 2021-04-07 | 2022-08-05 | 南京工业大学 | Synthetic method of five-membered oxygen heterocyclic compound |
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