JP2008184433A - Method for synthesizing metallole ring-containing compound - Google Patents
Method for synthesizing metallole ring-containing compound Download PDFInfo
- Publication number
- JP2008184433A JP2008184433A JP2007019971A JP2007019971A JP2008184433A JP 2008184433 A JP2008184433 A JP 2008184433A JP 2007019971 A JP2007019971 A JP 2007019971A JP 2007019971 A JP2007019971 A JP 2007019971A JP 2008184433 A JP2008184433 A JP 2008184433A
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- JP
- Japan
- Prior art keywords
- group
- ring
- reaction
- metalol
- alkyl
- Prior art date
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000003402 intramolecular cyclocondensation reaction Methods 0.000 claims abstract description 5
- -1 phosphoryl group Chemical group 0.000 claims description 58
- 125000001424 substituent group Chemical group 0.000 claims description 33
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 19
- 125000000217 alkyl group Chemical group 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 16
- 229910052736 halogen Inorganic materials 0.000 claims description 16
- 150000002367 halogens Chemical class 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000007363 ring formation reaction Methods 0.000 claims description 16
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000004104 aryloxy group Chemical group 0.000 claims description 15
- 125000003342 alkenyl group Chemical group 0.000 claims description 14
- 125000000304 alkynyl group Chemical group 0.000 claims description 14
- 125000003277 amino group Chemical group 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 10
- 125000002950 monocyclic group Chemical group 0.000 claims description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 10
- 238000006952 Enyne metathesis reaction Methods 0.000 claims description 9
- 125000005194 alkoxycarbonyloxy group Chemical group 0.000 claims description 9
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 9
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 claims description 9
- 125000005129 aryl carbonyl group Chemical group 0.000 claims description 9
- 125000005199 aryl carbonyloxy group Chemical group 0.000 claims description 9
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 9
- 125000000707 boryl group Chemical group B* 0.000 claims description 9
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 claims description 9
- 125000001651 cyanato group Chemical group [*]OC#N 0.000 claims description 9
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims description 9
- 125000000623 heterocyclic group Chemical group 0.000 claims description 9
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 9
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 9
- 125000000061 phosphanyl group Chemical group [H]P([H])* 0.000 claims description 9
- 125000005328 phosphinyl group Chemical group [PH2](=O)* 0.000 claims description 9
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims description 9
- 125000003638 stannyl group Chemical group [H][Sn]([H])([H])* 0.000 claims description 9
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 claims description 9
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 9
- 125000002947 alkylene group Chemical group 0.000 claims description 8
- 125000005529 alkyleneoxy group Chemical group 0.000 claims description 8
- 125000000732 arylene group Chemical group 0.000 claims description 8
- 125000005200 aryloxy carbonyloxy group Chemical group 0.000 claims description 8
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 claims description 8
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- 125000001261 isocyanato group Chemical group *N=C=O 0.000 claims description 7
- 125000005842 heteroatom Chemical group 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 238000005649 metathesis reaction Methods 0.000 claims description 4
- 238000006462 rearrangement reaction Methods 0.000 claims description 4
- 238000006884 silylation reaction Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 93
- 239000000243 solution Substances 0.000 description 70
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 52
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 26
- 230000002829 reductive effect Effects 0.000 description 25
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 17
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 14
- 150000003967 siloles Chemical class 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 239000012043 crude product Substances 0.000 description 11
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000012298 atmosphere Substances 0.000 description 7
- 238000004440 column chromatography Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000003287 optical effect Effects 0.000 description 5
- 239000012044 organic layer Substances 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 238000004809 thin layer chromatography Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 4
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008707 rearrangement Effects 0.000 description 4
- 238000001308 synthesis method Methods 0.000 description 4
- 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 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 3
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 239000011986 second-generation catalyst Substances 0.000 description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 description 3
- 235000011152 sodium sulphate Nutrition 0.000 description 3
- MIUPTFWVTVISEG-UHFFFAOYSA-M (2-bromophenyl)methyl-triphenylphosphanium;bromide Chemical compound [Br-].BrC1=CC=CC=C1C[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 MIUPTFWVTVISEG-UHFFFAOYSA-M 0.000 description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 description 2
- ZJWPKCADKDSSMP-UHFFFAOYSA-N 1-bromo-2-(2-methylprop-1-enyl)benzene Chemical compound CC(C)=CC1=CC=CC=C1Br ZJWPKCADKDSSMP-UHFFFAOYSA-N 0.000 description 2
- VQTBXXTYFVNUNT-UHFFFAOYSA-N 1-bromo-2-[2-(4-methylphenyl)ethynyl]benzene Chemical compound C1(=CC=C(C=C1)C#CC1=C(C=CC=C1)Br)C VQTBXXTYFVNUNT-UHFFFAOYSA-N 0.000 description 2
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 2
- OIRHKGBNGGSCGS-UHFFFAOYSA-N 1-bromo-2-iodobenzene Chemical compound BrC1=CC=CC=C1I OIRHKGBNGGSCGS-UHFFFAOYSA-N 0.000 description 2
- MIHGHJYKIRLHEG-UHFFFAOYSA-N 1-bromo-2-pent-1-ynylbenzene Chemical compound CCCC#CC1=CC=CC=C1Br MIHGHJYKIRLHEG-UHFFFAOYSA-N 0.000 description 2
- IBXNCJKFFQIKKY-UHFFFAOYSA-N 1-pentyne Chemical compound CCCC#C IBXNCJKFFQIKKY-UHFFFAOYSA-N 0.000 description 2
- 0 C=Cc1c(*C(c(cc2)ccc2C(*c2c(C=C)cccc2)=C)=C)cccc1 Chemical compound C=Cc1c(*C(c(cc2)ccc2C(*c2c(C=C)cccc2)=C)=C)cccc1 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- UHOVQNZJYSORNB-MZWXYZOWSA-N benzene-d6 Chemical compound [2H]C1=C([2H])C([2H])=C([2H])C([2H])=C1[2H] UHOVQNZJYSORNB-MZWXYZOWSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- DHHBWYHLBPWLKE-UHFFFAOYSA-N chloro-(2-ethenylphenyl)-dimethylsilane Chemical compound C[Si](C)(Cl)C1=CC=CC=C1C=C DHHBWYHLBPWLKE-UHFFFAOYSA-N 0.000 description 2
- MYOJVBNQQVJWHE-UHFFFAOYSA-N chloro-dimethyl-(2-phenylethynyl)silane Chemical compound C[Si](C)(Cl)C#CC1=CC=CC=C1 MYOJVBNQQVJWHE-UHFFFAOYSA-N 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 150000001923 cyclic compounds Chemical group 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010265 fast atom bombardment Methods 0.000 description 2
- ARNWQMJQALNBBV-UHFFFAOYSA-N lithium carbide Chemical compound [Li+].[Li+].[C-]#[C-] ARNWQMJQALNBBV-UHFFFAOYSA-N 0.000 description 2
- GNSLYOGEBCFYDE-UHFFFAOYSA-N lithium;ethynylbenzene Chemical compound [Li+].[C-]#CC1=CC=CC=C1 GNSLYOGEBCFYDE-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- PWYVVBKROXXHEB-UHFFFAOYSA-M trimethyl-[3-(1-methyl-2,3,4,5-tetraphenylsilol-1-yl)propyl]azanium;iodide Chemical compound [I-].C[N+](C)(C)CCC[Si]1(C)C(C=2C=CC=CC=2)=C(C=2C=CC=CC=2)C(C=2C=CC=CC=2)=C1C1=CC=CC=C1 PWYVVBKROXXHEB-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- LZSYGJNFCREHMD-UHFFFAOYSA-N 1-bromo-2-(bromomethyl)benzene Chemical compound BrCC1=CC=CC=C1Br LZSYGJNFCREHMD-UHFFFAOYSA-N 0.000 description 1
- SRXJYTZCORKVNA-UHFFFAOYSA-N 1-bromoethenylbenzene Chemical compound BrC(=C)C1=CC=CC=C1 SRXJYTZCORKVNA-UHFFFAOYSA-N 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- SCVJRXQHFJXZFZ-KVQBGUIXSA-N 2-amino-9-[(2r,4s,5r)-4-hydroxy-5-(hydroxymethyl)oxolan-2-yl]-3h-purine-6-thione Chemical compound C1=2NC(N)=NC(=S)C=2N=CN1[C@H]1C[C@H](O)[C@@H](CO)O1 SCVJRXQHFJXZFZ-KVQBGUIXSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- KSZVOXHGCKKOLL-UHFFFAOYSA-N 4-Ethynyltoluene Chemical compound CC1=CC=C(C#C)C=C1 KSZVOXHGCKKOLL-UHFFFAOYSA-N 0.000 description 1
- RMJRMKDNJPHTBP-UHFFFAOYSA-N CC[Si+]1(CC)c2ccccc2C=C1c1ccccc1 Chemical compound CC[Si+]1(CC)c2ccccc2C=C1c1ccccc1 RMJRMKDNJPHTBP-UHFFFAOYSA-N 0.000 description 1
- RJXMFXOKKXTMFC-UHFFFAOYSA-N CC[SiH-]1(CC)c2ccccc2C=C1c1ccccc1 Chemical compound CC[SiH-]1(CC)c2ccccc2C=C1c1ccccc1 RJXMFXOKKXTMFC-UHFFFAOYSA-N 0.000 description 1
- CBFXLBHFVNJBRS-UHFFFAOYSA-N C[S+]1c2ccccc2C=C1c1ccccc1 Chemical compound C[S+]1c2ccccc2C=C1c1ccccc1 CBFXLBHFVNJBRS-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical class [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- BIFFEGYIEAXUBH-UHFFFAOYSA-M [Br-].[Mg+]C(=C)C1=CC=CC=C1 Chemical compound [Br-].[Mg+]C(=C)C1=CC=CC=C1 BIFFEGYIEAXUBH-UHFFFAOYSA-M 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000000451 chemical ionisation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- KMVZWUQHMJAWSY-UHFFFAOYSA-N chloro-dimethyl-prop-2-enylsilane Chemical compound C[Si](C)(Cl)CC=C KMVZWUQHMJAWSY-UHFFFAOYSA-N 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- CNXMDTWQWLGCPE-UHFFFAOYSA-N ditert-butyl-(2-phenylphenyl)phosphane Chemical group CC(C)(C)P(C(C)(C)C)C1=CC=CC=C1C1=CC=CC=C1 CNXMDTWQWLGCPE-UHFFFAOYSA-N 0.000 description 1
- 239000012039 electrophile Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000006328 exo cyclization reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005227 gel permeation chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000000752 ionisation method Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- LROBJRRFCPYLIT-UHFFFAOYSA-M magnesium;ethyne;bromide Chemical compound [Mg+2].[Br-].[C-]#C LROBJRRFCPYLIT-UHFFFAOYSA-M 0.000 description 1
- 238000006263 metalation reaction Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000006476 reductive cyclization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- BWHDROKFUHTORW-UHFFFAOYSA-N tritert-butylphosphane Chemical compound CC(C)(C)P(C(C)(C)C)C(C)(C)C BWHDROKFUHTORW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、電子輸送性を有する発光材料、電子機能材料および光機能材料として適用可能なメタロール環含有化合物を容易に合成することのできる合成方法に関するものである。 The present invention relates to a synthesis method capable of easily synthesizing a metalol ring-containing compound applicable as a light-emitting material having electron transport properties, an electronic functional material, and an optical functional material.
シクロペンタジエン構造中にＳｉを有するシロール（シラシクロペンタジエン）誘導体は電子受容性を示すことが知られており、例えば、非特許文献１〜２には、シロール誘導体を有機ＥＬ素子に利用した例が報告されている。このようなシロール誘導体を機能性材料として用途展開する場合、目的に応じてシロール誘導体に様々な置換基を導入し、機能性材料としての性能を制御することが、今後重要となってくる。 Silole (silacyclopentadiene) derivatives having Si in the cyclopentadiene structure are known to exhibit electron accepting properties. For example, Non-Patent Documents 1 and 2 include examples in which silole derivatives are used in organic EL devices. It has been reported. When such a silole derivative is used as a functional material, it will be important in the future to introduce various substituents into the silole derivative according to the purpose and control the performance as the functional material.
上記観点から、近年になって、種々の置換基を有するシロール誘導体の合成方法が開発されている。例えば、特許文献１〜３には、２，５−反応性置換基含有シロール等が開示されているが、このシロールの３位および４位は、水素やフェニル基等の非反応性置換基でなければならないため、種々のシロール誘導体が合成できる方法とは言えない。また、これらの特許文献１〜３に開示される方法ではアルカリ金属やアルカリ金属錯体を用いているが、これらは空気中の酸素・窒素・水分等と高い反応性を有しているため、製造工程が煩雑になったり、特殊な製造装置を用いなければならない。 From the above viewpoint, in recent years, methods for synthesizing silole derivatives having various substituents have been developed. For example, Patent Documents 1 to 3 disclose 2,5-reactive substituent-containing siloles and the like, but the 3-position and 4-position of this silole are non-reactive substituents such as hydrogen and phenyl groups. Therefore, it cannot be said that various silole derivatives can be synthesized. Moreover, although the alkali metal and the alkali metal complex are used in the methods disclosed in these patent documents 1 to 3, since these have high reactivity with oxygen, nitrogen, moisture, etc. in the air, they are manufactured. A process becomes complicated and a special manufacturing apparatus must be used.
さらに、特許文献４には、スピロシロールの合成法が記載されているが、ジベンゾシロールに限定されている。特許文献５には、ジシラン化合物にチタニウムアルコキシドとハロゲンを反応させて、ビス置換シリル化物を得た後、シロール誘導体を得る方法が開示されているが、ビス置換シリル化合物を得る際に低温反応が必要であったり、反応時間が長いという問題があった。特許文献６にもシロール誘導体が記載されているが、原料を得る際のビフェニル化合物とリチウム化合物との低温メタル化反応では強力なアニオンが発生するため、導入できる置換基に制限があった。 Furthermore, Patent Document 4 describes a method for synthesizing spirosilole, but is limited to dibenzosilole. Patent Document 5 discloses a method in which a disilane compound is reacted with a titanium alkoxide and a halogen to obtain a bis-substituted silylated product, and then a silole derivative is obtained. However, when a bis-substituted silyl compound is obtained, a low-temperature reaction is disclosed. There was a problem that it was necessary or the reaction time was long. Patent Document 6 also describes a silole derivative. However, since a strong anion is generated in the low-temperature metalation reaction between a biphenyl compound and a lithium compound when obtaining a raw material, there are limitations on the substituents that can be introduced.
また、特許文献７には、分子内還元的環化反応によって得られるシロール誘導体が記載されているが、環化反応のためには、金属還元剤や還元により生成するジアニオン中間体を捕捉するための求電子剤が必要となり、反応が複雑である。
上述したように、従来のシロール誘導体の合成法で用いられる原料には、取扱い性に劣っていたり、合成が困難である等の問題がある。また、得られるシロール誘導体もある程度、限定された構造のものしか得られていない。 As described above, the raw materials used in the conventional methods for synthesizing silole derivatives have problems such as poor handling and difficulty in synthesis. Also, the silole derivatives obtained are only limited to a certain extent.
そこで本発明では、置換基による修飾が容易で、反応自体も簡便な、シロール等のメタロール環含有化合物の合成方法を提供することを課題として掲げた。 Therefore, the present invention has been made to provide a method for synthesizing a metalol ring-containing compound such as silole, which can be easily modified with a substituent and can be easily reacted.
上記課題を解決し得た本発明のメタロール環含有化合物の合成方法は、メタロール環を有さず、３個以上の不飽和結合を有する原料化合物から、２個以上の不飽和結合が関与する分子内閉環反応を利用してメタロール環を有する化合物を合成するところに要旨を有する。 The method for synthesizing a metalol ring-containing compound of the present invention that has solved the above problems is a molecule that does not have a metalol ring and that involves two or more unsaturated bonds from a raw material compound that has three or more unsaturated bonds. The gist is that a compound having a metalol ring is synthesized using an internal ring-closing reaction.
分子内閉環反応の一つは、下記式で示される閉環メタセシス反応である。 One of the intramolecular ring closure reactions is a ring closure metathesis reaction represented by the following formula.
分子内閉環反応は、下記式で示されるエンインメタセシス反応または骨格転位反応であってもよい。 The intramolecular ring closure reaction may be an ene-in metathesis reaction or a skeletal rearrangement reaction represented by the following formula.
分子内閉環反応として、下記式で示されるトランス−アリルシリル化またはトランス−アリルゲルミル化反応を採用することも可能である。 It is also possible to employ a trans-allyl silylation or trans-allyl gellation reaction represented by the following formula as the intramolecular ring closure reaction.
上記各式において、Ｍは、ＳｉまたはＧｅを意味する。 In the above formulas, M means Si or Ge.
Ｘ1，Ｙ1，Ｘ2，Ｙ2，Ｘ3，Ｙ3は、それぞれ同一もしくは異なって、水素、ハロゲン、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキニル基、アルケニル基、アミノ基を意味する。 X 1 , Y 1 , X 2 , Y 2 , X 3 , Y 3 are the same or different and are each hydrogen, halogen, alkyl group, aryl group, alkoxy group, aryloxy group, alkynyl group, alkenyl group, amino group Means.
Ｒ1〜Ｒ22は、それぞれ同一または異なって、置換基を有していてもよい、アルキレン基、アリーレン基、アルキレンオキシ基、アリーレンオキシ基、ＳｉおよびＧｅのいずれかを介した／または介さない、水素、ハロゲン、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキニル基、アルケニル基、パーフルオロアルキル基、アルキルカルボニル基、アリールカルボニル基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルオキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、ニトロ基、ニトロソ基、アゾ基、スルファニル基、スルホニル基、スルフィニル基、ホスファニル基、ホスフィニル基、ホスホリル基、シアノ基、イソシアノ基、シアナト基、イソシアナト基、チオシアナト基、カルバモイル基、ホルミル基、ホルミルオキシ基、シリル基、スタンニル基、ボリル基またはヘテロ環基を意味する。 R 1 to R 22 are the same as or different from each other, and may have a substituent, and / or not via any of an alkylene group, an arylene group, an alkyleneoxy group, an aryleneoxy group, Si and Ge. , Hydrogen, halogen, alkyl group, aryl group, alkoxy group, aryloxy group, alkynyl group, alkenyl group, perfluoroalkyl group, alkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyl Oxy group, aryloxycarbonyloxy group, amino group, nitro group, nitroso group, azo group, sulfanyl group, sulfonyl group, sulfinyl group, phosphanyl group, phosphinyl group, phosphoryl group, cyano group, isocyano group, cyanato group, isocyanato group , Thio Anat group, a carbamoyl group, a formyl group, a formyloxy group, a silyl group means a stannyl group, a boryl group, or a heterocyclic group.
また上記式で表される各化合物において、Ｘ1，Ｙ1，Ｘ2，Ｙ2，Ｘ3，Ｙ3，Ｒ1〜Ｒ22のうち隣接する基がある場合、これらはそれぞれ共同して、ヘテロ原子を介し／または介さずに、単環状／または縮合環状に結合していてもよい。ここで、上記単環状または縮合環状に結合した基は、さらに、アルキル基、アリール基、アルコキシ基、アリールオキシ基、ＳｉおよびＧｅのいずれかを介し／または介さずに、水素、ハロゲン、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキニル基、アルケニル基、パーフルオロアルキル基、アルキルカルボニル基、アリールカルボニル基、アルキルカルボニルオキシ基、アリールカルボニルオキシ基、アルキルオキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、ニトロ基、ニトロソ基、アゾ基、スルファニル基、スルホニル基、スルフィニル基、ホスファニル基、ホスフィニル基、ホスホリル基、シアノ基、イソシアノ基、シアナト基、イソシアナト基、チオシアナト基、カルバモイル基、ホルミル基、ホルミルオキシ基、シリル基、スタンニル基、ボリル基またはヘテロ環基を、置換基として有していてもよい。 In addition, in each compound represented by the above formula, when there are adjacent groups among X 1 , Y 1 , X 2 , Y 2 , X 3 , Y 3 , R 1 to R 22 , these are combined, You may couple | bond with the monocyclic / or condensed ring via the hetero atom. Here, the group bonded to the monocyclic or condensed ring further includes a hydrogen, halogen, or alkyl group with or without an alkyl group, an aryl group, an alkoxy group, an aryloxy group, Si, or Ge. , Aryl group, alkoxy group, aryloxy group, alkynyl group, alkenyl group, perfluoroalkyl group, alkylcarbonyl group, arylcarbonyl group, alkylcarbonyloxy group, arylcarbonyloxy group, alkyloxycarbonyloxy group, aryloxycarbonyloxy Group, amino group, nitro group, nitroso group, azo group, sulfanyl group, sulfonyl group, sulfinyl group, phosphanyl group, phosphinyl group, phosphoryl group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, carbamoyl group Formyl group, a formyloxy group, a silyl group, stannyl group, a boryl group, or a heterocyclic group, which may have a substituent.
本発明の合成方法は、原料化合物が有する不飽和結合を利用した分子内閉環反応によりメタロール環を形成するため、特殊な製造装置を必要とせず、常温〜加熱下といったマイルドな条件で容易にメタロール環含有化合物を合成することができる。また、分子内閉環反応に対して不活性な置換基を原料化合物に導入しておけば、これらの置換基を持つメタロール環含有化合物を合成することができるため、置換基を適宜選択することで機能材料としての性能を自由にコントロールすることができる。さらに、原料化合物は１種類でよいため、数種類の原料化合物を用いる場合と比べて質量バランス（等量）を合致させる必要がなく、過剰に加えた試薬を失活させる等の後処理工程も不要なため、簡便に反応を行えるようになった。 In the synthesis method of the present invention, a metalol ring is formed by an intramolecular ring-closing reaction using an unsaturated bond of a raw material compound, so that a special production apparatus is not required and a metalol can be easily obtained under mild conditions such as normal temperature to heating. Ring-containing compounds can be synthesized. In addition, if a substituent inactive to the intramolecular ring-closing reaction is introduced into the raw material compound, a metalol ring-containing compound having these substituents can be synthesized. The performance as a functional material can be freely controlled. Furthermore, since only one type of raw material compound is required, it is not necessary to match the mass balance (equal amount) as compared with the case of using several types of raw material compounds, and there is no need for a post-processing step such as deactivation of excessively added reagents. Therefore, the reaction can be easily performed.
本発明の合成方法で得られるメタロール環含有化合物は、有機ＥＬ素子の電子輸送層や、発光材料等の電気・光機能材料として適用可能である。 The metalol ring-containing compound obtained by the synthesis method of the present invention can be applied as an electron transport layer of an organic EL device or an electric / optical functional material such as a light emitting material.
本発明の合成方法は、メタロール環を有さず、３個以上の不飽和結合を有する原料化合物から、２個以上の不飽和結合が関与する分子内閉環反応を利用してメタロール環を有する化合物を合成するものである。この分子内閉環反応は４種類あり、（ａ）閉環メタセシス、（ｂ）エンインメタセシス、（ｃ）骨格転位および（ｄ）トランス−アリルシリル化（またはゲルミル化）である。 The synthesis method of the present invention includes a compound having a metalol ring by utilizing an intramolecular ring-closing reaction involving two or more unsaturated bonds from a raw material compound having three or more unsaturated bonds and having no metalol ring. Is synthesized. There are four types of intramolecular ring-closing reactions: (a) ring-closing metathesis, (b) ene-in metathesis, (c) skeletal rearrangement and (d) trans-allylsilylation (or gelmylation).
（ａ）閉環メタセシス反応
閉環メタセシス反応は、下記に記載した反応である。
(A) Ring-closing metathesis reaction The ring-closing metathesis reaction is a reaction described below.
上記閉環メタセシスの反応機構は、下式に従うものと考えられる。なお、簡単のために閉環反応に寄与しない置換基は省略した。 The reaction mechanism of the ring-closing metathesis is considered to follow the following formula. For simplicity, substituents that do not contribute to the ring closure reaction are omitted.
ここで、Ｍ'は触媒に由来する金属原子である。この反応においては、グラブス(Grubbs)第二世代触媒として知られているルテニウム触媒、またはSchrock触媒として知られているモリブデン触媒がいずれも使用可能である。 Here, M ′ is a metal atom derived from the catalyst. In this reaction, either a ruthenium catalyst known as a Grubbs second generation catalyst or a molybdenum catalyst known as a Schrock catalyst can be used.
上記閉環メタセシスにおいて、原料化合物として用いられるのは前記した（１）の化合物である。Ｍは、ＳｉまたはＧｅである。よって、本発明でいうメタロール環は、シロール環またはゲルモール環である。Ｘ1とＹ1は、それぞれ同一もしくは異なって、水素、ハロゲン、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキニル基、アルケニル基、アミノ基を意味する。 In the ring-closing metathesis, the compound (1) is used as a raw material compound. M is Si or Ge. Therefore, the metalol ring referred to in the present invention is a silole ring or a gelmol ring. X 1 and Y 1 are the same or different and each represents hydrogen, halogen, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkynyl group, an alkenyl group, or an amino group.
上記化合物（１）のＲ1〜Ｒ8は、それぞれ同一または異なって、置換基を有していてもよい、アルキレン基（−Ｒ−）、アリーレン基（−Ａｒ−）、アルキレンオキシ基（−ＯＲ−）、アリーレンオキシ基（−ＯＡｒ−）、Ｓｉ、Ｇｅのいずれかを介した／または介さない、水素、ハロゲン（−Ｆ，−Ｃｌ，−Ｂｒ，−Ｉ）、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキニル基（−Ｃ≡Ｃ）、アルケニル基（−Ｃ＝Ｃ）、パーフルオロアルキル基（−Ｒｆ）、アルキルカルボニル基（−Ｃ（＝Ｏ）Ｒ）、アリールカルボニル基（−Ｃ（＝Ｏ）Ａｒ）、アルキルカルボニルオキシ基（−ＯＣ（＝Ｏ）Ｒ）、アリールカルボニルオキシ基（−ＯＣ（＝Ｏ）Ａｒ）、アルキルオキシカルボニルオキシ基（−ＯＣ（＝Ｏ）ＯＲ）、アリールオキシカルボニルオキシ基（−ＯＣ（＝Ｏ）ＯＡｒ）、アミノ基（−ＮＨ2）、ニトロ基（−ＮＯ2）、ニトロソ基（−ＮＯ）、アゾ基（−Ｎ＝ＮＨ）、スルファニル基（−ＳＲ）、スルホニル基（−ＳＯ2Ｒ）、スルフィニル基（−Ｓ（＝Ｏ）Ｒ）、ホスファニル基（−ＰＲ2）、ホスフィニル基（−Ｐ（＝Ｏ）Ｒ2）、ホスホリル基（−Ｐ（＝Ｏ）（ＯＲ）2）、シアノ基（−ＣＮ）、イソシアノ基（−ＮＣ）、シアナト基（−ＯＣＮ）、イソシアナト基（−ＮＣＯ）、チオシアナト基（−ＳＣＮ）、カルバモイル基（−Ｃ（＝Ｏ）ＮＨ2）、ホルミル基（−ＣＨＯ）、ホルミルオキシ基（−ＯＣ（＝Ｏ）Ｈ）、シリル（Ｓｉ）基、スタンニル（Ｓｎ）基、ボリル（Ｂ）基またはヘテロ環基を意味する。 R 1 to R 8 of the compound (1) are the same or different and may have a substituent, an alkylene group (—R—), an arylene group (—Ar—), an alkyleneoxy group (— OR-), aryleneoxy group (-OAr-), Si, Ge, and / or without hydrogen, halogen (-F, -Cl, -Br, -I), alkyl group, aryl group, Alkoxy group, aryloxy group, alkynyl group (—C≡C), alkenyl group (—C═C), perfluoroalkyl group (—Rf), alkylcarbonyl group (—C (═O) R), arylcarbonyl group (-C (= O) Ar), alkylcarbonyloxy group (-OC (= O) R), arylcarbonyloxy group (-OC (= O) Ar), alkyloxycarbonyloxy group (-OC (= O) O ), An aryloxycarbonyl group (-OC (= O) OAr) , amino group (-NH 2), nitro group (-NO 2), nitroso group (-NO), an azo group (-N = NH), sulfanyl Group (—SR), sulfonyl group (—SO 2 R), sulfinyl group (—S (═O) R), phosphanyl group (—PR 2 ), phosphinyl group (—P (═O) R 2 ), phosphoryl group (—P (═O) (OR) 2 ), cyano group (—CN), isocyanato group (—NC), cyanato group (—OCN), isocyanato group (—NCO), thiocyanato group (—SCN), carbamoyl group (—C (═O) NH 2 ), formyl group (—CHO), formyloxy group (—OC (═O) H), silyl (Si) group, stannyl (Sn) group, boryl (B) group or hetero Means a cyclic group.
上記例示において、Ｒは、炭素数１〜１８程度までのアルキル基を意味し、直鎖状、分岐したもの、脂環構造を有するものの、いずれも含まれる。具体的には、メチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｓｅｃ−ブチル、ｔｅｒｔ−ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、シクロプロピル、シクロブチル、シクロペンチル、シクロヘキシル等である。また、Ａｒは、芳香族性を有する５員環以上の環式化合物であって、ベンゼン、ナフタレン等の炭素環（ビフェニル等も含む）、Ｏ，Ｎ，Ｓ等を含む複素環等を意味する。この定義は、以下においても同様である。これらの環式化合物は置換基を有していてもよい。有していてもよい置換基は、上記Ｒ1〜Ｒ8の例として示した基がそのまま該当する。 In the above exemplification, R means an alkyl group having about 1 to 18 carbon atoms, and includes any of linear, branched and alicyclic structures. Specifically, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. . Ar is a cyclic compound having 5 or more members having aromaticity, and means a carbocyclic ring such as benzene or naphthalene (including biphenyl), a heterocyclic ring including O, N, S or the like. . This definition is the same in the following. These cyclic compounds may have a substituent. As the substituent which may be included, the groups shown as examples of R 1 to R 8 are applicable as they are.
上記化合物（１）のＸ1，Ｙ1，Ｒ1〜Ｒ8のいずれか２以上の隣接する基が互いに結合して（共同して）、ヘテロ原子を介し／または介さずに、単環状／または縮合環状に結合した構造を採ることもできる。ヘテロ原子の例としては、Ｎ，Ｏ，Ｓ等が挙げられ、これらの原子が環の中に組み込まれていてもよい。環を構成している場合は、その環は上述の場合と同様に置換基を有していてもよい。 Any two or more adjacent groups of X 1 , Y 1 , R 1 to R 8 of the compound (1) are bonded to each other (in cooperation), and may be monocyclic / Alternatively, a structure in which condensed rings are bonded can also be adopted. Examples of heteroatoms include N, O, S, etc., and these atoms may be incorporated into the ring. In the case of constituting a ring, the ring may have a substituent as described above.
ここで、Ｘ1，Ｙ1，Ｒ1〜Ｒ8が、共同して単環状／または縮合環状に結合した構造を採る場合とは、例えば、下記のような例である。なお、環の形成に寄与しない置換基は省略している。 Here, the case where X 1 , Y 1 , R 1 to R 8 jointly take a monocyclic / or condensed cyclic structure is, for example, the following example. Note that substituents that do not contribute to ring formation are omitted.
例１ 上記式（１）において、Ｘ1とＹ1、Ｒ2とＲ3が環を形成している例。化合物（１）のＲ2およびＲ3とが芳香環を構成している場合は、閉環メタセシスによってベンゾメタロールを得ることができる。 Example 1 In the above formula (1), X 1 and Y 1 , R 2 and R 3 form a ring. When R 2 and R 3 of the compound (1) form an aromatic ring, a benzometall can be obtained by ring-closing metathesis.
例２ 上記式（１）において、Ｘ1とＹ1、Ｒ2とＲ3が環を形成している例 Example 2 In the above formula (1), X 1 and Y 1 , R 2 and R 3 form a ring
例３ 上記式（１）において、Ｘ1とＲ2、Ｒ2とＲ3が環を形成している例 Example 3 In the above formula (1), X 1 and R 2 , R 2 and R 3 form a ring
例４ 上記式（１）において、Ｒ3とＲ4が環を形成している例 Example 4 In the above formula (1), R 3 and R 4 form a ring
例５ 上記式（１）において、Ｒ2とＲ3、Ｒ5とＲ6が環を形成している例 Example 5 In the above formula (1), R 2 and R 3 , R 5 and R 6 form a ring
例６ 上記式（１）において、Ｒ1とＲ8、Ｒ2とＲ3、Ｒ4とＲ5が環を形成している例 Example 6 In the above formula (1), R 1 and R 8 , R 2 and R 3 , R 4 and R 5 form a ring
もちろん、上記例１〜例６以外の構成で環を形成していても良い。 Of course, the ring may be formed with a configuration other than the above Examples 1 to 6.
閉環メタセシス反応における目的生成物であるメタロール環含有化合物（２）にはＲ1〜Ｒ4が残るので、メタロール環含有化合物に導入したい置換基を、Ｒ1〜Ｒ4のいずれか（複数可）としておくとよい。 Since R 1 to R 4 remain in the metalol ring-containing compound (2), which is the target product in the ring-closing metathesis reaction, the substituent to be introduced into the metalol ring-containing compound is any one of R 1 to R 4 (s). It is good to keep it.
閉環メタセシス反応で得ることのできるメタロール環含有化合物（２）の具体例を下記に示すが、もちろんこれらに限定されるわけではない。 Specific examples of the metalol ring-containing compound (2) that can be obtained by the ring-closing metathesis reaction are shown below, but of course not limited thereto.
また、下記のスキームに従う閉環メタセシス反応によりメタロール環含有化合物（２）を得ることも可能である。 It is also possible to obtain a metalol ring-containing compound (2) by a ring-closing metathesis reaction according to the following scheme.
上記閉環メタセシス反応は、溶媒中で行ってもよい。用い得る溶媒としては、トルエン、ｍ−キシレン、オクタン、シクロヘキサン等の炭化水素類；１，２−ジクロロエタン、１，１，２，２，−テトラクロロエタン、１，２−ジクロロベンゼン等のハロゲン化炭化水素類；テトラヒドロフラン、テトラヒドロピラン、ジブチルエーテル、１，４−ジオキサン等のエーテル類等が挙げられる。なお、閉環メタセシス反応は、窒素などの不活性ガス雰囲気下で行うことが望ましい。 The ring-closing metathesis reaction may be performed in a solvent. Solvents that can be used include hydrocarbons such as toluene, m-xylene, octane and cyclohexane; halogenated carbonization such as 1,2-dichloroethane, 1,1,2,2, -tetrachloroethane and 1,2-dichlorobenzene. Hydrogens; Ethers such as tetrahydrofuran, tetrahydropyran, dibutyl ether, 1,4-dioxane and the like can be mentioned. The ring-closing metathesis reaction is desirably performed in an inert gas atmosphere such as nitrogen.
反応温度は特に限定されないが、０〜２００℃が好ましい。室温（２３℃）でも充分、反応が進行する。より好ましい温度の上限は１８０℃、さらに好ましい上限は１４５℃である。反応時間も特に限定されないが、１〜６０時間が好ましい。反応後は、カラム等を用い、常法によって精製する。 Although reaction temperature is not specifically limited, 0-200 degreeC is preferable. The reaction proceeds sufficiently even at room temperature (23 ° C.). A more preferable upper limit of the temperature is 180 ° C, and a more preferable upper limit is 145 ° C. Although reaction time is not specifically limited, 1 to 60 hours are preferable. After the reaction, it is purified by a conventional method using a column or the like.
（ｂ）エンインメタセシス反応
エンインメタセシス反応は、下記に記載した反応である。
(B) Enyne metathesis reaction The enyne metathesis reaction is a reaction described below.
エンインメタセシスの反応機構は、下式に従うものと考えられる。なお、簡単のために閉環反応に寄与しない置換基は省略した。 The reaction mechanism of enyne metathesis is considered to follow the following formula. For simplicity, substituents that do not contribute to the ring closure reaction are omitted.
上式においてもＭ'は触媒に由来する金属原子である。この反応においては、グラブス(Grubbs)第二世代触媒として知られているルテニウム触媒、（Ｐｈ3Ｐ）ＡｕＮＴｆ2［トリフェニルホスフィン金ビス（トリフルオロメタンスルホニル）イミド］等のカチオン性の金触媒、ＰｔＣｌ2等の白金触媒が効果的である。 Also in the above formula, M ′ is a metal atom derived from the catalyst. In this reaction, a ruthenium catalyst known as a Grubbs second generation catalyst, a cationic gold catalyst such as (Ph 3 P) AuNTf 2 [triphenylphosphine gold bis (trifluoromethanesulfonyl) imide], PtCl A platinum catalyst such as 2 is effective.
上記エンインメタセシスにおいて、原料化合物として用いられるのは前記した（４）の化合物である。上記化合物（４）のＭ，Ｘ2，Ｙ2，Ｒ9〜Ｒ14の意味は、前記化合物（１）におけるＭ，Ｘ1，Ｙ1，Ｒ1〜Ｒ8と、それぞれ全く同じ意味である。 In the enyne metathesis, the compound (4) is used as a raw material compound. The meanings of M, X 2 , Y 2 , R 9 to R 14 in the compound (4) are exactly the same as M, X 1 , Y 1 , R 1 to R 8 in the compound (1). .
上記エンインメタセシス反応によれば、不飽和二重結合が含まれた置換基を有するメタロール環含有化合物が生成する。エンインメタセシス反応は、閉環メタセシス反応の場合と同様にして、行うことができる（溶媒、温度、時間、雰囲気等）。反応後は、常法によって精製する。 According to the above enyne metathesis reaction, a metalol ring-containing compound having a substituent containing an unsaturated double bond is produced. The enyne metathesis reaction can be carried out in the same manner as in the ring-closing metathesis reaction (solvent, temperature, time, atmosphere, etc.). After the reaction, it is purified by a conventional method.
（ｃ）骨格転位
骨格転位反応は、見かけ上は、エンインメタセシス反応と同じ原料化合物（４）から、同じ目的生成物（５）と、同じ副生成物（６）が生成する。よって、原料化合物の説明は省略する。ただし、反応機構はエンインメタセシス反応とは異なっており、下式に従うものと考えられる。なお、簡単のために閉環反応に寄与しない置換基は省略した。
(C) Skeletal rearrangement In the skeletal rearrangement reaction, the same target product (5) and the same byproduct (6) are produced from the same raw material compound (4) as the ene-in metathesis reaction. Therefore, description of the raw material compound is omitted. However, the reaction mechanism is different from the enyne metathesis reaction, and is considered to follow the following formula. For simplicity, substituents that do not contribute to the ring closure reaction are omitted.
骨格転位では、最初にｅｘｏ環化が起こり、上記のように反応が進む。上式においてもＭ’は触媒に由来する金属原子である。この反応においては、（Ｐｈ3Ｐ）ＡｕＮＴｆ2等のカチオン性の金触媒、ＰｔＣｌ2等の白金触媒が効果的である。骨格転位反応も閉環メタセシス反応の場合と同様に行うことができる（溶媒、温度、時間、雰囲気等）。反応後は、常法によって精製する。 In skeletal rearrangement, exo cyclization occurs first and the reaction proceeds as described above. Also in the above formula, M ′ is a metal atom derived from the catalyst. In this reaction, a cationic gold catalyst such as (Ph 3 P) AuNTf 2 and a platinum catalyst such as PtCl 2 are effective. The skeletal rearrangement reaction can also be performed in the same manner as in the ring-closing metathesis reaction (solvent, temperature, time, atmosphere, etc.). After the reaction, it is purified by a conventional method.
（ｄ）トランス−アリルシリル化（またはゲルミル化）
トランス−アリルシリル化（またはゲルミル化）反応は、以下のスキームに従う。
(D) trans-allylsilylation (or gelmylation)
The trans-allylsilylation (or gelmylation) reaction follows the following scheme.
トランス−アリルシリル化（またはゲルミル化）の反応機構は、下式に従うものと推測される。閉環反応に寄与しない置換基は省略した。 The reaction mechanism of trans-allylsilylation (or gelmylation) is assumed to follow the following formula. Substituents that do not contribute to the ring closure reaction are omitted.
上式においてもＭ'は触媒に由来する金属原子である。この反応においては、（Ｐｈ3Ｐ）ＡｕＮＴｆ2、（ｔ−Ｂｕ）3ＰＡｕＮＴｆ2［トリ（ｔｅｒｔ−ブチル）ホスフィン金ビス（トリフルオロメタンスルホニル）イミド］、（Ｌ）ＡｕＮＴｆ2［Ｌは２−（ジ−ｔｅｒｔ−ブチルホスフィノ）ビフェニルである。］等の金触媒が効果的である。 Also in the above formula, M ′ is a metal atom derived from the catalyst. In this reaction, (Ph 3 P) AuNTf 2 , (t-Bu) 3 PAuNTf 2 [tri (tert-butyl) phosphine gold bis (trifluoromethanesulfonyl) imide], (L) AuNTf 2 [L is 2- ( Di-tert-butylphosphino) biphenyl. ] Is effective.
上記トランス−アリルシリル化（またはゲルミル化）において、原料化合物として用いられるのは、前記した（７）の化合物である。上記化合物（７）のＭ，Ｘ3，Ｙ3，Ｒ15〜Ｒ22の意味は、前記化合物（１）におけるＭ，Ｘ1，Ｙ1，Ｒ1〜Ｒ8と、それぞれ同じ意味である。環構造を有する化合物（７）の例を下記に示す。なお、環の形成に寄与しない置換基は省略している。 In the trans-allylsilylation (or gelmylation), the compound (7) is used as a raw material compound. The meanings of M, X 3 , Y 3 , R 15 to R 22 in the compound (7) are the same as M, X 1 , Y 1 , R 1 to R 8 in the compound (1), respectively. Examples of the compound (7) having a ring structure are shown below. Note that substituents that do not contribute to ring formation are omitted.
例１ 上記式（７）において、Ｒ16とＲ17、Ｒ20とＲ22（またはＲ21）が環を形成している例。 Example 1 In the above formula (7), R 16 and R 17 , R 20 and R 22 (or R 21 ) form a ring.
例２ 上記式（７）において、Ｒ16とＲ17、Ｒ21とＲ22が環を形成している例。 Example 2 In the above formula (7), R 16 and R 17 , R 21 and R 22 form a ring.
例３ 上記式（７）において、Ｒ16とＲ17、Ｒ19とＲ21が環を形成している例。 Example 3 In the above formula (7), R 16 and R 17 , R 19 and R 21 form a ring.
例４ 上記式（７）において、Ｒ16とＲ17、Ｒ18とＲ19が環を形成している例。 Example 4 In the above formula (7), R 16 and R 17 , R 18 and R 19 form a ring.
もちろん、上記例１〜例４以外の構成で環を形成していても良い。 Of course, you may form the ring by structures other than the said Examples 1-4.
上記トランス−アリルシリル化（またはゲルミル化）反応によっても、不飽和二重結合が含まれた置換基を有するメタロール環含有化合物が生成する。トランス−アリルシリル化（またはゲルミル化）反応によって得ることのできるメタロール環含有化合物（８）の具体例を下記に示すが、もちろんこれらに限定されるわけではない。 Also by the trans-allylsilylation (or gelmylation) reaction, a metalol ring-containing compound having a substituent containing an unsaturated double bond is produced. Specific examples of the metalol ring-containing compound (8) that can be obtained by the trans-allylsilylation (or gelmylation) reaction are shown below, but of course not limited thereto.
トランス−アリルシリル化（またはゲルミル化）反応は、閉環メタセシス反応の場合と同様にして、行うことができる（溶媒、温度、時間、雰囲気等）。反応後は、常法によって精製する。 The trans-allylsilylation (or gelmylation) reaction can be carried out in the same manner as in the ring-closing metathesis reaction (solvent, temperature, time, atmosphere, etc.). After the reaction, it is purified by a conventional method.
なお、各種反応に用いられる原料化合物は、ハライドを出発原料としてリチウム化し、Ｒ2ＳｉＺ2（Ｚはハロゲン）でシリル化することにより得ることができる。具体的には、以下のように行えばよい。 The raw material compounds used in various reactions can be obtained by lithiation using halide as a starting material and silylation with R 2 SiZ 2 (Z is halogen). Specifically, it may be performed as follows.
１．例えば、−７８℃のハライドのテトラヒドロフラン（ＴＨＦ）溶液に、ｎ−ブチルリチウムのヘキサン溶液を滴下し、１時間程度撹拌して、ハライドをリチオ化する。
２．上記リチオ化物を含む溶液を、−７８℃のＲ2ＳｉＺ2のＴＨＦ溶液に滴下して、室温（２２℃）下で１０〜３０時間程度、撹拌する。
３．反応液にヘキサンを加えて反応を停止させる。
４．揮発性物質を減圧留去し、シリル化物を得る。
５．−７８℃のアルキンのＴＨＦ溶液に、ｎ−ブチルリチウムのヘキサン溶液を滴下し、１時間程度撹拌して、リチウムアセチリドを発生させる。
６．前記シリル化物のＴＨＦ溶液を上記５のリチウムアセチリド溶液に滴下して、室温（２２℃）下で１０〜３０時間程度、撹拌する。
７．反応液に冷水を加えて反応を停止させる。
８．エーテル抽出後、乾燥、精製等を行えば、ジエン化合物が得られる。
1. For example, a hexane solution of n-butyllithium is dropped into a tetrahydrofuran (THF) solution of halide at −78 ° C. and stirred for about 1 hour to lithiate the halide.
2. The solution containing the lithiated product is dropped into a THF solution of R 2 SiZ 2 at −78 ° C. and stirred at room temperature (22 ° C.) for about 10 to 30 hours.
3. Hexane is added to the reaction solution to stop the reaction.
4). Volatile substances are distilled off under reduced pressure to obtain a silylated product.
5. A hexane solution of n-butyllithium is dropped into a THF solution of alkyne at −78 ° C., and the mixture is stirred for about 1 hour to generate lithium acetylide.
6). The THF solution of the silylated product is dropped into the lithium acetylide solution of 5 above and stirred at room temperature (22 ° C.) for about 10 to 30 hours.
7). Cold water is added to the reaction solution to stop the reaction.
8). A diene compound can be obtained by performing drying, purification, etc. after ether extraction.
以下実施例によって本発明を詳細に説明するが、本発明の範囲はこれら実施例のみに限定されるものではない。なお、以下の実施例で用いた測定装置および測定条件は、次の通りである。また、式中、Ｂｕはブチル基を、Ｍｅはメチル基を、Ｐｈはフェニル基を、Ｐｒはプロピル基をそれぞれ表す。 EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the scope of the present invention is not limited only to these examples. The measurement apparatus and measurement conditions used in the following examples are as follows. In the formula, Bu represents a butyl group, Me represents a methyl group, Ph represents a phenyl group, and Pr represents a propyl group.
［1ＨＮＭＲ］
重クロロホルム（ＣＤＣｌ3）または重ベンゼン（Ｃ6Ｄ6）を用いて、バリアン社製の「Ｇｅｍｉｎｉ ２０００」により測定した。化学シフトは、テトラメチルシラン（ＳｉＭｅ4）から低磁場側での１００万分の１（ｐｐｍ；δスケール）として記録し、ＮＭＲ溶媒（ＣＤＣｌ3：δ７．２６；Ｃ6Ｄ6：δ７．１６）中の残留水素核を参照とした。
[ 1 HNMR]
Measurement was carried out using “Gemini 2000” manufactured by Varian, using deuterated chloroform (CDCl 3 ) or deuterated benzene (C 6 D 6 ). Chemical shifts are recorded from tetramethylsilane (SiMe 4 ) as parts per million (ppm; δ scale) on the low magnetic field side, and NMR solvent (CDCl 3 : δ 7.26; C 6 D 6 : δ 7.16). Reference was made to residual hydrogen nuclei.
［高分解能質量分析計（ＨＲＭＳ）］
日本電子（株）社製の「JMS−SX102A」、「JMS−MS700」、「JMS−BU250」により、化学イオン化法（ＣＩ）、電子イオン化法（ＥＩ）または高速原子衝撃法（ＦＡＢ）を用いて測定した。
[High-resolution mass spectrometer (HRMS)]
Chemical ionization method (CI), electron ionization method (EI), or fast atom bombardment method (FAB) is used with “JMS-SX102A”, “JMS-MS700”, “JMS-BU250” manufactured by JEOL Ltd. Measured.
原料合成例１：ジメチル（1-フェニルビニル）（2-ビニルフェニル）シラン Raw Material Synthesis Example 1: Dimethyl (1-phenylvinyl) (2-vinylphenyl) silane
窒素雰囲気下、ｏ−ブロモスチレン10 gのテトラヒドロフラン溶液55 ｍLにｎ−ブチルリチウム（1.53 M）ヘキサン溶液43 mLを−78℃で滴下し、さらに1時間攪拌を続けた。反応溶液をジクロロジメチルシラン20 mLのテトラヒドロフラン溶液55 mLに0℃で滴下し、室温で15時間攪拌を続けた。揮発性物質を減圧下留去した後、ヘキサンを加え、吸引ろ過した。ろ液を減圧下濃縮し、残さ物を減圧蒸留することでクロロジメチル（2-ビニルフェニル）シラン6.5 gを得た。 Under a nitrogen atmosphere, 43 mL of n-butyllithium (1.53 M) hexane solution was added dropwise to 55 mL of a tetrahydrofuran solution of 10 g of o-bromostyrene at −78 ° C., and stirring was further continued for 1 hour. The reaction solution was added dropwise to 55 mL of a tetrahydrofuran solution of 20 mL of dichlorodimethylsilane at 0 ° C., and stirring was continued at room temperature for 15 hours. Volatile substances were distilled off under reduced pressure, hexane was added, and suction filtration was performed. The filtrate was concentrated under reduced pressure, and the residue was distilled under reduced pressure to obtain 6.5 g of chlorodimethyl (2-vinylphenyl) silane.
窒素雰囲気下、マグネシウム0.68 gのテトラヒドロフラン溶液20 mLにα-ブロモスチレン5 gのテトラヒドロフラン溶液30mLを室温で滴下し、さらに3時間攪拌を続けた。生成した臭化（１-フェニルビニル）マグネシウム溶液をクロロジメチル（2-ビニルフェニル）シラン2 gのテトラヒドロフラン溶液10 mLに0℃で滴下し、さらに10時間攪拌を続けた。揮発性物質を減圧下留去した後、残さ物に飽和塩化アンモニウム水溶液を加え、ヘキサンで抽出し、有機層を硫酸ナトリウムで乾燥した。ヘキサンを減圧下留去した後、粗生成物をカラムクロマトグラフィー（ヘキサン）、次いでゲル浸透クロマトグラフィーにより精製し、ジメチル（1-フェニルビニル）（2-ビニルフェニル）シラン0.5 gを得た。 Under a nitrogen atmosphere, 30 mL of a tetrahydrofuran solution of 5 g of α-bromostyrene was added dropwise to 20 mL of a tetrahydrofuran solution of 0.68 g of magnesium at room temperature, and stirring was further continued for 3 hours. The produced (1-phenylvinyl) magnesium bromide solution was added dropwise to 10 mL of a tetrahydrofuran solution of 2 g of chlorodimethyl (2-vinylphenyl) silane at 0 ° C., and stirring was further continued for 10 hours. After distilling off volatile substances under reduced pressure, a saturated aqueous ammonium chloride solution was added to the residue, followed by extraction with hexane, and the organic layer was dried over sodium sulfate. After hexane was distilled off under reduced pressure, the crude product was purified by column chromatography (hexane) and then gel permeation chromatography to obtain 0.5 g of dimethyl (1-phenylvinyl) (2-vinylphenyl) silane.
1H NMR (CDCl3) の結果：
δ 0.45 (s, 6H), 5.22 (dd, J = 11.0, 1.2 Hz,1H), 5.61 (dd, J = 17.1, 0.9 Hz,1H), 5.68 (d, J = 3.0 Hz, 1H), 6.01 (d, J = 3.0 Hz, 1H), 7.07-7.27 (m, 7H), 7.37 (t, J = 7.2 Hz, 1H), 7.55 (d, J = 5.1 Hz, 2H).
1 H NMR (CDCl 3 ) results:
δ 0.45 (s, 6H), 5.22 (dd, J = 11.0, 1.2 Hz, 1H), 5.61 (dd, J = 17.1, 0.9 Hz, 1H), 5.68 (d, J = 3.0 Hz, 1H), 6.01 ( d, J = 3.0 Hz, 1H), 7.07-7.27 (m, 7H), 7.37 (t, J = 7.2 Hz, 1H), 7.55 (d, J = 5.1 Hz, 2H).
原料合成例２：ジメチル（フェニルエチニル）（２-ビニルフェニル）シラン Raw Material Synthesis Example 2: Dimethyl (phenylethynyl) (2-vinylphenyl) silane
窒素雰囲気下、フェニルアセチレン3.37 gのテトラヒドロフラン溶液30 mLにｎ−ブチルリチウム（1.6 M）ヘキサン溶液25 mLを−78℃で滴下し、（フェニルエチニル）リチウムを調製した。ジクロロジメチルシラン17.6 gのテトラヒドロフラン溶液30 mLに（フェニルエチニル）リチウムのテトラヒドロフラン溶液を−78℃で滴下した。反応液にヘキサンを加え、ろ過し、ろ液を減圧下濃縮した。残さ物を真空蒸留することによりクロロジメチル（フェニルエチニル）シラン2.0 gを得た。 Under a nitrogen atmosphere, 25 mL of n-butyllithium (1.6 M) hexane solution was added dropwise to 30 mL of a tetrahydrofuran solution of 3.37 g of phenylacetylene at −78 ° C. to prepare (phenylethynyl) lithium. A tetrahydrofuran solution of (phenylethynyl) lithium was added dropwise to 30 mL of a tetrahydrofuran solution of 17.6 g of dichlorodimethylsilane at −78 ° C. Hexane was added to the reaction solution and filtered, and the filtrate was concentrated under reduced pressure. The residue was vacuum distilled to obtain 2.0 g of chlorodimethyl (phenylethynyl) silane.
窒素雰囲気下、o-ブロモスチレン3.0 gのテトラヒドロフラン溶液20 mLにｎ−ブチルリチウム（1.6 M）ヘキサン溶液25 mLを−78℃で滴下した。２時間後、反応溶液にクロロジメチル（フェニルエチニル）シラン2.0 gのテトラヒドロフラン溶液15 mLを−78℃で滴下した。室温で終夜撹拌後、テトラヒドロフランを減圧下留去した。残さ物に飽和塩化アンモニウム水溶液を加え、ヘキサン−酢酸エチル混合溶媒で抽出した。有機層をフロリジル（登録商標）ショートカラムに通した後、カラムクロマトグラフィーにより精製し、ジメチル（フェニルエチニル）（２-ビニルフェニル）シラン2.24 gを得た。 Under a nitrogen atmosphere, 25 mL of n-butyllithium (1.6 M) hexane solution was added dropwise at −78 ° C. to 20 mL of a tetrahydrofuran solution of 3.0 g of o-bromostyrene. Two hours later, 15 mL of a tetrahydrofuran solution of 2.0 g of chlorodimethyl (phenylethynyl) silane was added dropwise to the reaction solution at −78 ° C. After stirring overnight at room temperature, tetrahydrofuran was distilled off under reduced pressure. A saturated aqueous ammonium chloride solution was added to the residue, and the mixture was extracted with a hexane-ethyl acetate mixed solvent. The organic layer was passed through a Florisil (registered trademark) short column and then purified by column chromatography to obtain 2.24 g of dimethyl (phenylethynyl) (2-vinylphenyl) silane.
1H NMR (CDCl3)の結果：
δ 0.54 (s, 6H), 5.32 (dd, J = 11.1, 1.2 Hz, 1H), 5.67 (dd, J = 17.1, 1.2 Hz, 1H), 7.24-7.42 (m, 6H), 7.46-7.51 (m, 2H), 7.56-7.61 (m, 1H), 7.69-7.74 (m, 1H)
1 H NMR (CDCl 3 ) results:
δ 0.54 (s, 6H), 5.32 (dd, J = 11.1, 1.2 Hz, 1H), 5.67 (dd, J = 17.1, 1.2 Hz, 1H), 7.24-7.42 (m, 6H), 7.46-7.51 (m , 2H), 7.56-7.61 (m, 1H), 7.69-7.74 (m, 1H)
原料合成例３：エチニルジメチル（2-イソブテニルフェニル）シラン Raw material synthesis example 3: Ethynyldimethyl (2-isobutenylphenyl) silane
o-ブロモベンジルブロミド12.5 g，トリフェニルホスフィン16.4 gのアセトン溶液150 mLを12時間加熱還流した。生成した沈殿をろ別し、アセトンで洗浄した。減圧乾燥により臭化o-ブロモベンジルトリフェニルホスホニウム25.9 gを得た。 150 mL of an acetone solution of 12.5 g of o-bromobenzyl bromide and 16.4 g of triphenylphosphine was heated to reflux for 12 hours. The produced precipitate was filtered off and washed with acetone. By drying under reduced pressure, 25.9 g of o-bromobenzyltriphenylphosphonium bromide was obtained.
臭化o-ブロモベンジルトリフェニルホスホニウム20.5 g、アセトン2.9 mLのエタノール溶液40 mLにナトリウムエトキシド2.86 gのエタノール溶液40 mLを室温下で滴下した。終夜撹拌後、エタノールを減圧下留去し、残さ物をカラムクロマトグラフィー（ヘキサン：酢酸エチル＝20:1）により精製し、1-ブロモ-2-（2-メチル-1-プロペニル）ベンゼン6.00 gを得た。 40 mL of an ethanol solution of 2.86 g of sodium ethoxide was added dropwise to 40 mL of an ethanol solution of 20.5 g of o-bromobenzyltriphenylphosphonium bromide and 2.9 mL of acetone at room temperature. After stirring overnight, ethanol was distilled off under reduced pressure, and the residue was purified by column chromatography (hexane: ethyl acetate = 20: 1) to give 6.00 g of 1-bromo-2- (2-methyl-1-propenyl) benzene. Got.
窒素雰囲気下、1-ブロモ-2-（2-メチル-1-プロペニル）ベンゼン12.7 gのテトラヒドロフラン溶液60 mLにｎ−ブチルリチウム（1.6 M）ヘキサン溶液45 mLを−78℃で滴下し［2-(2-メチル-１-プロペニル)フェニル］リチウムを調製した。ジクロロジメチルシラン21.7 mLのテトラヒドロフラン溶液60 mLに（2-イソブテニルフェニル）リチウムのテトラヒドロフラン溶液を−78℃で滴下した。テトラヒドロフランを減圧下留去後、蒸留によりクロロジメチル（2-イソブテニルフェニル）シラン3.75 gを得た。 Under a nitrogen atmosphere, 45 mL of n-butyllithium (1.6 M) hexane solution was added dropwise to 60 mL of a tetrahydrofuran solution of 12.7 g of 1-bromo-2- (2-methyl-1-propenyl) benzene at −78 ° C. [2- (2-Methyl-1-propenyl) phenyl] lithium was prepared. A tetrahydrofuran solution of (2-isobutenylphenyl) lithium in 60 mL of a tetrahydrofuran solution of 21.7 mL of dichlorodimethylsilane was added dropwise at −78 ° C. Tetrahydrofuran was distilled off under reduced pressure, and 3.75 g of chlorodimethyl (2-isobutenylphenyl) silane was obtained by distillation.
クロロジメチル（2-イソブテニルフェニル）シラン3.75 gのジエチルエーテル溶液17 mLに臭化エチニルマグネシウム（0.5 M）テトラヒドロフラン溶液50 mLを0℃で滴下した。5時間撹拌後、反応溶液に飽和塩化アンモニウム水溶液を加えヘキサンで抽出した。有機層を硫酸ナトリウムで乾燥し、揮発性物質を減圧下留去した。粗生成物をカラムクロマトグラフィー（ヘキサン：酢酸エチル＝100:1）により精製し、エチニルジメチル（2-イソブテニルフェニル）シラン2.25 gを得た。 To 17 mL of a diethyl ether solution of 3.75 g of chlorodimethyl (2-isobutenylphenyl) silane, 50 mL of an ethinylmagnesium bromide (0.5 M) tetrahydrofuran solution was added dropwise at 0 ° C. After stirring for 5 hours, a saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with hexane. The organic layer was dried over sodium sulfate and the volatile material was removed under reduced pressure. The crude product was purified by column chromatography (hexane: ethyl acetate = 100: 1) to obtain 2.25 g of ethynyldimethyl (2-isobutenylphenyl) silane.
1H NMR (CDCl3)の結果：
δ 0.41 (s, 6H), 1.64 (s, 3H), 1.88 (s, 3H), 2.51 (s, 1H), 6.53 (s, 1H), 7.12-7.18 (m, 1H), 7.18-7.26 (m, 1H), 7.32-7.39 (m, 1H), 7.71-7.76 (m, 1H)
1 H NMR (CDCl 3 ) results:
δ 0.41 (s, 6H), 1.64 (s, 3H), 1.88 (s, 3H), 2.51 (s, 1H), 6.53 (s, 1H), 7.12-7.18 (m, 1H), 7.18-7.26 (m , 1H), 7.32-7.39 (m, 1H), 7.71-7.76 (m, 1H)
原料合成例４：アリルジメチル［2-（p-トリルエチニル）フェニル］シラン Raw Material Synthesis Example 4: Allyldimethyl [2- (p-tolylethynyl) phenyl] silane
窒素雰囲気下、ジクロロビス（トリフェニルホスフィン）パラジウム（II）906 mg、ヨウ化銅（Ｉ）410 mg，2-ブロモヨードベンゼン12.2 gを含むトリエチルアミン懸濁液210 mLに1-エチニル-４-メチルベンゼン5.01 gのトリエチルアミン溶液70 mLを室温下で滴下した。２時間撹拌した後、反応溶液に飽和塩化アンモニウム水溶液を加え、ジエチルエーテルで抽出した。有機層を飽和食塩水、水の順で洗った後、硫酸ナトリウムで乾燥した。揮発性物質を減圧下留去し、得られた粗生成物をエタノールから再結晶し、1-ブロモ-2-（p-トリルエチニル）ベンゼン9.95 gを得た。 1-ethynyl-4-methylbenzene was added to 210 mL of triethylamine suspension containing 906 mg of dichlorobis (triphenylphosphine) palladium (II), 410 mg of copper (I) iodide, and 12.2 g of 2-bromoiodobenzene under nitrogen atmosphere. 70 mL of 5.01 g of triethylamine solution was added dropwise at room temperature. After stirring for 2 hours, a saturated aqueous ammonium chloride solution was added to the reaction solution, and the mixture was extracted with diethyl ether. The organic layer was washed with saturated brine and water in that order, and then dried over sodium sulfate. Volatile substances were distilled off under reduced pressure, and the resulting crude product was recrystallized from ethanol to obtain 9.95 g of 1-bromo-2- (p-tolylethynyl) benzene.
窒素雰囲気下、1-ブロモ-2-（p-トリルエチニル）ベンゼン3.71gのテトラヒドロフラン溶液30 mLにｎ−ブチルリチウム（1.6 M）ヘキサン溶液11.6 mLを−78℃で滴下した。１時間後、アリルクロロジメチルシラン3.3 mLを加え、徐々に室温に戻した。揮発性物質を減圧下で留去した後、粗生成物をカラムクロマトグラフィー（ヘキサン：酢酸エチル＝100:1）で精製し、アリルジメチル［2-（p-トリルエチニル）フェニル］シラン3.74 gを得た。 Under a nitrogen atmosphere, 11.6 mL of n-butyllithium (1.6 M) hexane solution was added dropwise at −78 ° C. to 30 mL of a tetrahydrofuran solution of 3.71 g of 1-bromo-2- (p-tolylethynyl) benzene. After 1 hour, 3.3 mL of allylchlorodimethylsilane was added, and the temperature was gradually returned to room temperature. After distilling off the volatile substances under reduced pressure, the crude product was purified by column chromatography (hexane: ethyl acetate = 100: 1) to obtain 3.74 g of allyldimethyl [2- (p-tolylethynyl) phenyl] silane. Obtained.
1H NMR (CDCl3)の結果：
δ 0.49 (s, 6H), 2.09 (dd, J = 7.9, 1.1 Hz, 2H), 2.42 (s, 3H), 4.87-4.98 (m, 2H), 5.88 (ddt, J = 17.0, 10.1, 7.9 Hz, 1H), 7.23 (d, J = 7.9 Hz, 2H), 7.32-7.42 (m, 2H), 7.50 (d, J = 8.0 Hz, 2H), 7.55-7.64 (m, 2H)
HRMS（EI）の結果：
C20H22Si (M+)：理論値：290.1491 ； 実測値：290.1490
1 H NMR (CDCl 3 ) results:
δ 0.49 (s, 6H), 2.09 (dd, J = 7.9, 1.1 Hz, 2H), 2.42 (s, 3H), 4.87-4.98 (m, 2H), 5.88 (ddt, J = 17.0, 10.1, 7.9 Hz , 1H), 7.23 (d, J = 7.9 Hz, 2H), 7.32-7.42 (m, 2H), 7.50 (d, J = 8.0 Hz, 2H), 7.55-7.64 (m, 2H)
HRMS (EI) results:
C 20 H 22 Si (M + ): Theoretical value: 290.1491; Found: 290.1490
原料合成例５：ジメチル（2-メタリル）［2-（1-ペンチニル）フェニル］シラン Raw Material Synthesis Example 5: Dimethyl (2-methallyl) [2- (1-pentynyl) phenyl] silane
窒素雰囲気下、2-ブロモヨードベンゼン5 g、ジクロロビス（トリフェニルホスフィン）パラジウム（ＩＩ）266 mg、ヨウ化銅（Ｉ）172 mgをトリエチルアミン溶液90 mL中、室温下5分間攪拌した。この混合物に1-ペンチン1.35 gのトリエチルアミン溶液30 mLを0℃で滴下した後、室温で7時間攪拌し、さらに1-ペンチン0.27 gを加え、室温で14時間攪拌を続けた。反応溶液を減圧下濃縮し、ヘキサンを加え、吸引ろ過した。ろ液を減圧下濃縮し、粗生成物をカラムクロマトグラフィー（ヘキサン）で精製し、1-ブロモ-2-（1-ペンチニル）ベンゼン3 gを得た。 Under a nitrogen atmosphere, 5 g of 2-bromoiodobenzene, 266 mg of dichlorobis (triphenylphosphine) palladium (II), and 172 mg of copper (I) iodide were stirred in 90 mL of a triethylamine solution at room temperature for 5 minutes. To this mixture, 30 mL of a triethylamine solution of 1.35 g of 1-pentyne was added dropwise at 0 ° C., followed by stirring at room temperature for 7 hours. Further, 0.27 g of 1-pentyne was added, and stirring was continued at room temperature for 14 hours. The reaction solution was concentrated under reduced pressure, hexane was added, and suction filtration was performed. The filtrate was concentrated under reduced pressure, and the crude product was purified by column chromatography (hexane) to obtain 3 g of 1-bromo-2- (1-pentynyl) benzene.
窒素雰囲気下、1-ブロモ-2-（1-ペンチニル）ベンゼン2.2 gのテトラヒドロフラン溶液17 mLにｎ−ブチルリチウム（1.55 M）ヘキサン溶液17 mLを-78℃で滴下し、1時間攪拌した。反応溶液をジクロロジメチルシラン2.4 mLのテトラヒドロフラン溶液17 mLに-78℃で滴下し、さらに室温で11時間攪拌した。反応液にヘキサンを加え、グラスフィルターで吸引ろ過した。ろ液を減圧下濃縮し、クロロジメチル［2-（1-ペンチニル）フェニル］シラン2.58 gを得た。 Under a nitrogen atmosphere, 17 mL of n-butyllithium (1.55 M) hexane solution was added dropwise to 17 mL of a tetrahydrofuran solution of 2.2 g of 1-bromo-2- (1-pentynyl) benzene at −78 ° C. and stirred for 1 hour. The reaction solution was added dropwise to 17 mL of a tetrahydrofuran solution of 2.4 mL of dichlorodimethylsilane at −78 ° C., and further stirred at room temperature for 11 hours. Hexane was added to the reaction solution and suction filtered through a glass filter. The filtrate was concentrated under reduced pressure to obtain 2.58 g of chlorodimethyl [2- (1-pentynyl) phenyl] silane.
窒素雰囲気下、マグネシウム12 gのジエチルエーテル溶液60 mLに塩化β−メタリル9.0 gのジエチルエーテル溶液30 mLを0℃で滴下し、0℃で1時間、室温で1.5時間攪拌した後、30分間静置した。生成した塩化β−メタリルマグネシウム溶液をクロロジメチル［2-（1-ペンチニル）フェニル］シラン2.58 gのテトラヒドロフラン溶液30 mLに-78℃で滴下し、室温で15時間攪拌した。反応溶液に飽和塩化アンモニウム水溶液100 mLをゆっくり加え、ジエチルエーテルで抽出し、有機層を硫酸マグネシウムで乾燥し、揮発性物質を減圧下留去した。粗生成物をカラムクロマトグラフィー（ヘキサン）で精製し、ジメチル（2-メタリル）［2-（1-ペンチニル）フェニル］シラン1.0 gを得た。 Under a nitrogen atmosphere, 30 mL of diethyl ether solution of 9.0 g of β-methallyl chloride was added dropwise to 60 mL of diethyl ether solution of 12 g of magnesium at 0 ° C, and the mixture was stirred at 0 ° C for 1 hour and at room temperature for 1.5 hours, and then allowed to stand for 30 minutes. I put it. The resulting β-methallylmagnesium chloride solution was added dropwise to 30 mL of a tetrahydrofuran solution of 2.58 g of chlorodimethyl [2- (1-pentynyl) phenyl] silane at −78 ° C. and stirred at room temperature for 15 hours. Saturated aqueous ammonium chloride solution (100 mL) was slowly added to the reaction solution, and the mixture was extracted with diethyl ether. The organic layer was dried over magnesium sulfate, and the volatile material was evaporated under reduced pressure. The crude product was purified by column chromatography (hexane) to obtain 1.0 g of dimethyl (2-methallyl) [2- (1-pentynyl) phenyl] silane.
1H NMR (CDCl3)の結果：
δ 0.42 (s, 6H), 1.09 (t, J = 7.2 Hz, 3H), 1.66 (s, 3H), 1.70 (sext, J = 7.2 Hz, 2H), 2.03 (s, 2H), 2.45 (t, J = 7.2 Hz, 2H), 4.52 (s, 1H), 4.61-4.62 (m, 1H), 7.24-7.34 (m, 2H), 7.45-7.49 (m, 2H)
HRMS (EI)の結果：
C17H24Si (M+)：理論値：256.1647 ； 実測値：256.1650
1 H NMR (CDCl 3 ) results:
δ 0.42 (s, 6H), 1.09 (t, J = 7.2 Hz, 3H), 1.66 (s, 3H), 1.70 (sext, J = 7.2 Hz, 2H), 2.03 (s, 2H), 2.45 (t, J = 7.2 Hz, 2H), 4.52 (s, 1H), 4.61-4.62 (m, 1H), 7.24-7.34 (m, 2H), 7.45-7.49 (m, 2H)
HRMS (EI) results:
C 17 H 24 Si (M + ): Theoretical value: 256.1647; Found: 256.1650
実施例１：閉環メタセシスによる1,1,2-トリメチル-1-シラインデンの合成 Example 1: Synthesis of 1,1,2-trimethyl-1-cyleidene by ring-closing metathesis
窒素雰囲気下、Schrock触媒11.5 mgにジメチル（イソプロペニル）（2-ビニルフェニル）シラン65.6 mgのトルエン溶液6 mLを加え、室温下20時間攪拌した。反応溶液にヘキサンを加え、フロリジル（登録商標）でろ過し、ろ液を減圧下濃縮し、1,1,2-トリメチル-1-シラインデン46.4 mgを得た。 Under a nitrogen atmosphere, 6 mL of a toluene solution of 65.6 mg of dimethyl (isopropenyl) (2-vinylphenyl) silane was added to 11.5 mg of Schrock's catalyst, and the mixture was stirred at room temperature for 20 hours. Hexane was added to the reaction solution and filtered through Florisil (registered trademark), and the filtrate was concentrated under reduced pressure to obtain 46.4 mg of 1,1,2-trimethyl-1-cyleidene.
1H NMR (CDCl3) の結果：
δ 0.28 (s, 6H), 2.02 (d, J = 1.5 Hz, 3H), 6.86 (q, J = 1.5 Hz, 1H), 7.12 (t, J = 6.9 Hz, 2H), 7.25-7.30 (m, 1H), 7.46 (d, J = 6.9 Hz, 1H)
1 H NMR (CDCl 3 ) results:
δ 0.28 (s, 6H), 2.02 (d, J = 1.5 Hz, 3H), 6.86 (q, J = 1.5 Hz, 1H), 7.12 (t, J = 6.9 Hz, 2H), 7.25-7.30 (m, 1H), 7.46 (d, J = 6.9 Hz, 1H)
実施例２：閉環メタセシスによる1,1-ジメチル-2-フェニル-1-シラインデンの合成 Example 2: Synthesis of 1,1-dimethyl-2-phenyl-1-cyleidene by ring-closing metathesis
窒素雰囲気下、Schrock触媒12.5 mgにジメチル（1-フェニルビニル）（2-ビニルフェニル）シラン77.8 mgのトルエン溶液6 mLを加え、室温下2時間攪拌した。反応溶液にヘキサンを加え、フロリジル（登録商標）でろ過し、ろ液を減圧下濃縮し、1,1-ジメチル-2-フェニル-1-シラインデン58.5 mgを得た。 Under a nitrogen atmosphere, 6 mL of a toluene solution of 77.8 mg of dimethyl (1-phenylvinyl) (2-vinylphenyl) silane was added to 12.5 mg of Schrock's catalyst, and the mixture was stirred at room temperature for 2 hours. Hexane was added to the reaction solution and filtered through Florisil (registered trademark), and the filtrate was concentrated under reduced pressure to obtain 58.5 mg of 1,1-dimethyl-2-phenyl-1-cyleidene.
1H NMR (CDCl3)の結果：
δ 0.48 (s, 6H), 7.20-7.40 (m, 6H), 7.49-7.56 (m, 4H)
1 H NMR (CDCl 3 ) results:
δ 0.48 (s, 6H), 7.20-7.40 (m, 6H), 7.49-7.56 (m, 4H)
実施例３：エンインメタセシスによる1,1-ジメチル-2-(1-ペンテン-2-イル)-1-シラインデンの合成：1,1-ジメチル-2-メチレン-3-プロピル-1,2-ジヒドロ-1-シラナフタレンは副生成物 Example 3: Synthesis of 1,1-dimethyl-2- (1-penten-2-yl) -1-cyleidene by enyne metathesis: 1,1-dimethyl-2-methylene-3-propyl-1,2-dihydro -1-silanaphthalene is a by-product
窒素雰囲気下、Grubbs第二世代触媒12.7 mgにジメチル（１-ペンチニル）（2-ビニルフェニル）シラン67.8 mgのトルエン溶液1.5 mLを加え、80℃で20時間攪拌した。反応溶液にヘキサンを加え、フロリジル（登録商標）でろ過し、ろ液を減圧下濃縮した。粗生成物を薄層クロマトグラフィー（ヘキサン）で精製し、1,1-ジメチル-2-(1-ペンテン-2-イル)-1-シラインデン，1,1-ジメチル-2-メチレン-3-プロピル-1,2-ジヒドロ-1-シラナフタレンの混合物45.6 mgを得た。 Under a nitrogen atmosphere, 1.5 mL of a toluene solution of 67.8 mg of dimethyl (1-pentynyl) (2-vinylphenyl) silane was added to 12.7 mg of Grubbs second generation catalyst, and the mixture was stirred at 80 ° C. for 20 hours. Hexane was added to the reaction solution, filtered through Florisil (registered trademark), and the filtrate was concentrated under reduced pressure. The crude product was purified by thin layer chromatography (hexane) to give 1,1-dimethyl-2- (1-penten-2-yl) -1-cyleidene, 1,1-dimethyl-2-methylene-3-propyl 45.6 mg of a mixture of -1,2-dihydro-1-silanaphthalene was obtained.
1H NMR (CDCl3)の結果：
1,1-ジメチル-2-(1-ペンテン-2-イル)-1-シラインデン
δ 0.31 (s, 6H), 0.97 (t, J = 7.5 Hz, 3H), 1.59 (sext, J = 7.5 Hz, 2H), 2.43 (t, J = 7.8 Hz, 2H), 5.61 (d, J = 1.5 Hz, 1H), 6.03 (d, J = 1.5 Hz, 1H), 6.29 (s, 1H), 7.10-7.19 (m, 2H), 7.28-7.31 (m, 1H), 7.48 (d, J = 0.6 Hz, 1H)
1,1-ジメチル-2-メチレン-3-プロピル-1,2-ジヒドロ-1-シラナフタレン
δ 0.43 (s, 6H), 1.00 (t, J = 7.5 Hz, 3H), 1.61 (sext, J = 7.5 Hz, 2H), 2.40 (t, J = 7.8 Hz, 2H), 5.07 (s, 1H), 5.09 (s, 1H), 7.16 (s, 1H), 7.19-7.29 (m, 2H), 7.31-7.38 (m, 1H), 7.52-7.54 (m,1H)
1 H NMR (CDCl 3 ) results:
1,1-dimethyl-2- (1-penten-2-yl) -1-cyleideneδ 0.31 (s, 6H), 0.97 (t, J = 7.5 Hz, 3H), 1.59 (sext, J = 7.5 Hz, 2H), 2.43 (t, J = 7.8 Hz, 2H), 5.61 (d, J = 1.5 Hz, 1H), 6.03 (d, J = 1.5 Hz, 1H), 6.29 (s, 1H), 7.10-7.19 ( m, 2H), 7.28-7.31 (m, 1H), 7.48 (d, J = 0.6 Hz, 1H)
1,1-dimethyl-2-methylene-3-propyl-1,2-dihydro-1-silanaphthalene δ 0.43 (s, 6H), 1.00 (t, J = 7.5 Hz, 3H), 1.61 (sext, J = 7.5 Hz, 2H), 2.40 (t, J = 7.8 Hz, 2H), 5.07 (s, 1H), 5.09 (s, 1H), 7.16 (s, 1H), 7.19-7.29 (m, 2H), 7.31- 7.38 (m, 1H), 7.52-7.54 (m, 1H)
実施例４：骨格転位による2-イソブテニル-1,1-ジメチル-1-シラインデンの合成：2-イソプロピリデン-1,1-ジメチル-1,2-ジヒドロ-1-シラナフタレンは副生成物 Example 4: Synthesis of 2-isobutenyl-1,1-dimethyl-1-silylenedene by skeletal rearrangement: 2-isopropylidene-1,1-dimethyl-1,2-dihydro-1-silanaphthalene is a by-product
窒素雰囲気下、(PPh3)AuNTf214.7 mgにエチニルジメチル(2-イソブテニルフェニル)シラン84.0 mgのジクロロメタン溶液2 mLを加え、室温で7時間攪拌した。反応溶液にヘキサンを加え、フロリジル（登録商標）でろ過し、ろ液を減圧下濃縮した。粗生成物を薄層クロマトグラフィー（ヘキサン）で精製し、2-イソブテニル-1,1-ジメチル-1-シラインデン、2-イソプロピリデン-1,1-ジメチル-1,2-ジヒドロ-1-シラナフタレンの混合物62.4 mgを得た。 Under a nitrogen atmosphere, 2 mL of a dichloromethane solution of 84.0 mg of ethynyldimethyl (2-isobutenylphenyl) silane was added to 14.7 mg of (PPh 3 ) AuNTf 2 and stirred at room temperature for 7 hours. Hexane was added to the reaction solution, filtered through Florisil (registered trademark), and the filtrate was concentrated under reduced pressure. The crude product was purified by thin layer chromatography (hexane), and then 2-isobutenyl-1,1-dimethyl-1-silylenedene, 2-isopropylidene-1,1-dimethyl-1,2-dihydro-1-silanaphthalene Of 62.4 mg of was obtained.
1H NMR (CDCl3)の結果：
2-イソブテニル-1,1-ジメチル-1-シラインデン
δ 0.44 (s, 6H), 1.87 (s, 3H), 1.92 (s, 3H), 6.20 (s, 1H), 7.01 (s, 1H), 7.15-7.18 (m, 2H), 7.28-7.31 (m, 1H), 7.46 (d, J = 7.8 Hz, 1H).
2-イソプロピリデン-1,1-ジメチル-1,2-ジヒドロ-1-シラナフタレン
δ 0.42 (s, 6H), 1.96 (s, 3H), 2.06 (s, 3H), 6.20 (d, J = 10.8 Hz, 1H), 6.66 (d, J = 10.8 Hz, 1H), 7.10 (d, J = 7.5 Hz, 1H), 7.17 (t, J = 7.5 Hz, 1H), 7.24-7.29 (m, 1H), 7.48 (d, J = 6.9 Hz, 1H)
1 H NMR (CDCl 3 ) results:
2-isobutenyl-1,1-dimethyl-1-cyleideneδ 0.44 (s, 6H), 1.87 (s, 3H), 1.92 (s, 3H), 6.20 (s, 1H), 7.01 (s, 1H), 7.15 -7.18 (m, 2H), 7.28-7.31 (m, 1H), 7.46 (d, J = 7.8 Hz, 1H).
2-Isopropylidene-1,1-dimethyl-1,2-dihydro-1-silanaphthalene δ 0.42 (s, 6H), 1.96 (s, 3H), 2.06 (s, 3H), 6.20 (d, J = 10.8 Hz, 1H), 6.66 (d, J = 10.8 Hz, 1H), 7.10 (d, J = 7.5 Hz, 1H), 7.17 (t, J = 7.5 Hz, 1H), 7.24-7.29 (m, 1H), 7.48 (d, J = 6.9 Hz, 1H)
実施例５：トランス−アリルシリル化による3-アリル-1,1-ジメチル-2-プロピル-1-シラインデンの合成 Example 5: Synthesis of 3-allyl-1,1-dimethyl-2-propyl-1-silylene by trans-allylsilylation
アルゴンガス雰囲気下、[2-PhC6H4P(t-Bu)2]AuNTf27.0 mgに、アリルジメチル［2-（1-ペンチニル）フェニル］シラン72.7 mgのジクロロメタン溶液0.37 mLを添加した。9時間室温で攪拌し、揮発性物質を減圧留去した。得られた粗生成物を薄層クロマトグラフィー（ヘキサン）で精製し、3-アリル-1,1-ジメチル-2-プロピル-1-シラインデン70.7 mgを得た。 Under an argon gas atmosphere, 0.37 mL of a dichloromethane solution of 72.7 mg of allyldimethyl [2- (1-pentynyl) phenyl] silane was added to 7.0 mg of [2-PhC 6 H 4 P (t-Bu) 2 ] AuNTf 2 . The mixture was stirred for 9 hours at room temperature, and the volatile material was distilled off under reduced pressure. The obtained crude product was purified by thin layer chromatography (hexane) to obtain 70.7 mg of 3-allyl-1,1-dimethyl-2-propyl-1-cyleidene.
1H NMR (CDCl3)の結果：
δ 0.34 (s, 6H), 0.99 (t, J = 7.4 Hz, 3H), 1.56 (sext, J = 7.4 Hz, 2H), 2.42 (t, J = 7.4 Hz, 2H), 3.34 (dt, J = 5.7, 1.6 Hz, 2H), 5.01-5.14 (m, 2H), 5.79 (ddt, J = 17.1, 10.1, 5.7 Hz, 1H), 7.18 (dt, J = 6.8, 1.6 Hz, 1H), 7.29-7.37 (m, 2H), 7.55 (d, J = 6.8 Hz, 1H)
HRMS (EI)の結果：
C16H22Si (M+)：理論値：242.1491 ； 実測値：242.1493
1 H NMR (CDCl 3 ) results:
δ 0.34 (s, 6H), 0.99 (t, J = 7.4 Hz, 3H), 1.56 (sext, J = 7.4 Hz, 2H), 2.42 (t, J = 7.4 Hz, 2H), 3.34 (dt, J = 5.7, 1.6 Hz, 2H), 5.01-5.14 (m, 2H), 5.79 (ddt, J = 17.1, 10.1, 5.7 Hz, 1H), 7.18 (dt, J = 6.8, 1.6 Hz, 1H), 7.29-7.37 (m, 2H), 7.55 (d, J = 6.8 Hz, 1H)
HRMS (EI) results:
C 16 H 22 Si (M + ): Theoretical value: 242.1491; Found: 242.1493
実施例６：トランス−アリルシリル化による3-アリル-1,1-ジメチル-2-p-トリル-1-シラインデンの合成 Example 6: Synthesis of 3-allyl-1,1-dimethyl-2-p-tolyl-1-syleidene by trans-allylsilylation
アルゴンガス雰囲気下、[2-PhC6H4P(t-Bu)2]AuNTf214.0 mgに、アリルジメチル［2-（p-トリルエチニル）フェニル］シラン87.1 mgのジクロロメタン溶液0.37 mLを添加した。9時間室温で攪拌し、揮発性物質を減圧留去した。得られた粗生成物を薄層クロマトグラフィー（ヘキサン）で精製し、3-アリル-1,1-ジメチル-2-p-トリル-1-シラインデン65.2 mgを得た。 Under argon gas atmosphere, 0.37 mL of dichloromethane solution of 87.1 mg of allyldimethyl [2- (p-tolylethynyl) phenyl] silane was added to 14.0 mg of [2-PhC 6 H 4 P (t-Bu) 2 ] AuNTf 2 . The mixture was stirred for 9 hours at room temperature, and the volatile material was distilled off under reduced pressure. The obtained crude product was purified by thin layer chromatography (hexane) to obtain 65.2 mg of 3-allyl-1,1-dimethyl-2-p-tolyl-1-cyleidene.
1H NMR (CDCl3) の結果：
δ 0.37 (s, 6H), 2.38 (s, 3H), 3.33 (d, J = 5.4 Hz, 2H), 5.05-5.12 (m, 2H), 6.02 (ddt, J = 17.7, 9.8, 5.4 Hz, 1H), 7.10 (d, J = 8.1 Hz, 2H), 7.17-7.27 (m, 3H), 7.37-7.40 (m, 2H), 7.57 (d, J = 6.9 Hz, 1H)
HRMS (EI)の結果：
C20H22Si (M+)：理論値：290.1491 ； 実測値：290.1492
1 H NMR (CDCl 3 ) results:
δ 0.37 (s, 6H), 2.38 (s, 3H), 3.33 (d, J = 5.4 Hz, 2H), 5.05-5.12 (m, 2H), 6.02 (ddt, J = 17.7, 9.8, 5.4 Hz, 1H ), 7.10 (d, J = 8.1 Hz, 2H), 7.17-7.27 (m, 3H), 7.37-7.40 (m, 2H), 7.57 (d, J = 6.9 Hz, 1H)
HRMS (EI) results:
C 20 H 22 Si (M + ): Theoretical value: 290.1491; Found: 290.1492
実施例７：トランス−アリルシリル化による1,1-ジメチル-3-（2-メタリル）-2-プロピル-1-シラインデン Example 7: 1,1-Dimethyl-3- (2-methallyl) -2-propyl-1-sylinedene by trans-allylsilylation
アルゴンガス雰囲気下、[2-PhC6H4P(t-Bu)2]AuNTf27.0 mgに、ジメチル（2-メタリル）［2-（1-ペンチニル）フェニル］シラン76.9 mgのジクロロメタン溶液0.37 mLを添加した。9時間室温で攪拌し、揮発性物質を減圧留去した。得られた粗生成物を薄層クロマトグラフィー（ヘキサン）で精製し、1,1-ジメチル-3-（2-メタリル）-2-プロピル-1-シラインデン64.2 mgを得た。 Under argon gas atmosphere, [2-PhC 6 H 4 P (t-Bu) 2 ] AuNTf 2 7.0 mg and dimethyl (2-methallyl) [2- (1-pentynyl) phenyl] silane 76.9 mg in dichloromethane solution 0.37 mL Was added. The mixture was stirred for 9 hours at room temperature, and the volatile material was distilled off under reduced pressure. The obtained crude product was purified by thin layer chromatography (hexane) to obtain 64.2 mg of 1,1-dimethyl-3- (2-methallyl) -2-propyl-1-cyleidene.
1H NMR (CDCl3) の結果：
δ 0.31 (s, 6H), 0.96 (t, J = 7.6 Hz, 3H), 1.52 (sext, J = 7.6 Hz, 2H), 1.80 (s, 3H), 2,36 (t, J = 7.6 Hz, 2H), 3.23 (s, 2H), 4.64 (s, 1H), 4.74 (s, 1H), 7.14 (dt, J = 6.9, 1.2 Hz, 1H), 7.21-7.32 (m, 2H), 7.47 (d, J = 6.9 Hz, 1H).
HRMS (EI)の結果：
C17H24Si (M+)：理論値：256.1647 ； 実測値：256.1647
1 H NMR (CDCl 3 ) results:
δ 0.31 (s, 6H), 0.96 (t, J = 7.6 Hz, 3H), 1.52 (sext, J = 7.6 Hz, 2H), 1.80 (s, 3H), 2,36 (t, J = 7.6 Hz, 2H), 3.23 (s, 2H), 4.64 (s, 1H), 4.74 (s, 1H), 7.14 (dt, J = 6.9, 1.2 Hz, 1H), 7.21-7.32 (m, 2H), 7.47 (d , J = 6.9 Hz, 1H).
HRMS (EI) results:
C 17 H 24 Si (M + ): Theoretical value: 256.1647; Found: 256.1647
実施例８：トランス−アリルゲルミル化による3-アリル-1,1-ジメチル-2-プロピル-1-ゲルマインデンの合成 Example 8: Synthesis of 3-allyl-1,1-dimethyl-2-propyl-1-germaindene by trans-allyl gellation
1H NMR (CDCl3) の結果：
δ 0.49 (s, 6H), 0.96 (t, J = 7.5 Hz, 3H), 1.54 (sext, J = 7.5 Hz, 2H), 2.46 (t, J = 7.4 Hz, 2H), 3.33 (d, J = 5.7 Hz, 2H), 4.98-5.10 (m, 2H), 5.91 (ddt, J = 17.1, 10.5, 5.7 Hz, 1H), 7.15-7.20 (m, 1H), 7.30-7.31 (m, 2H), 7.50 (d, J = 6.9 Hz, 1H)
HRMS (EI)の結果：
C16H22Ge (M+)：理論値：288.0933 ； 実測値：288.0934
1 H NMR (CDCl 3 ) results:
δ 0.49 (s, 6H), 0.96 (t, J = 7.5 Hz, 3H), 1.54 (sext, J = 7.5 Hz, 2H), 2.46 (t, J = 7.4 Hz, 2H), 3.33 (d, J = 5.7 Hz, 2H), 4.98-5.10 (m, 2H), 5.91 (ddt, J = 17.1, 10.5, 5.7 Hz, 1H), 7.15-7.20 (m, 1H), 7.30-7.31 (m, 2H), 7.50 (d, J = 6.9 Hz, 1H)
HRMS (EI) results:
C 16 H 22 Ge (M + ): Theoretical value: 288.0933; Found: 288.0934
本発明法では容易にメタロール環含有化合物を合成することができるので、出発原料の置換基を適宜選択することで、得られるメタロール環含有化合物の性能を自由にコントロールすることができる。よって、得られたメタロール環含有化合物は、電子機器、例えば有機ＥＬ素子、太陽電池、コンデンサ、燃料電池、二次電池、センサー、ディテクター、光回路、光導波路、トランジスタ、電気回路などの構成部材、有機ＥＬ素子の中間層（正孔輸送層または電子輸送層等）、太陽電池の光電変換層等の電気・光機能材料として適用可能である。 Since the metalol ring-containing compound can be easily synthesized in the method of the present invention, the performance of the obtained metalol ring-containing compound can be freely controlled by appropriately selecting the substituent of the starting material. Therefore, the obtained metalol ring-containing compound is an electronic device, for example, an organic EL element, a solar cell, a capacitor, a fuel cell, a secondary battery, a sensor, a detector, an optical circuit, an optical waveguide, a transistor, an electric circuit, or the like, It can be applied as an electric / optical functional material such as an intermediate layer (such as a hole transport layer or an electron transport layer) of an organic EL element, a photoelectric conversion layer of a solar cell, or the like.
Claims (8)
The method for synthesizing a metalol ring-containing compound according to claim 7, wherein the trans-allyl silylation reaction or the trans-allyl gelylation reaction is a reaction represented by the following formula.
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| JP2007019971A JP2008184433A (en) | 2007-01-30 | 2007-01-30 | Method for synthesizing metallole ring-containing compound |
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| JP2007019971A JP2008184433A (en) | 2007-01-30 | 2007-01-30 | Method for synthesizing metallole ring-containing compound |
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| JP2008184433A true JP2008184433A (en) | 2008-08-14 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10290812B2 (en) | 2014-11-25 | 2019-05-14 | Samsung Electronics Co., Ltd. | Compound for organic photoelectric device and organic photoelectric device image sensor, and electronic device including the same |
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2007
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10290812B2 (en) | 2014-11-25 | 2019-05-14 | Samsung Electronics Co., Ltd. | Compound for organic photoelectric device and organic photoelectric device image sensor, and electronic device including the same |
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