JPH0730101B2 - 2,1,4-benzoxadisilane derivative and method for producing the same - Google Patents
2,1,4-benzoxadisilane derivative and method for producing the sameInfo
- Publication number
- JPH0730101B2 JPH0730101B2 JP2057277A JP5727790A JPH0730101B2 JP H0730101 B2 JPH0730101 B2 JP H0730101B2 JP 2057277 A JP2057277 A JP 2057277A JP 5727790 A JP5727790 A JP 5727790A JP H0730101 B2 JPH0730101 B2 JP H0730101B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- bis
- benzoxadisilane
- same
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 claims description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 8
- 150000002430 hydrocarbons Chemical group 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 150000003003 phosphines Chemical class 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000003905 agrochemical Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QAUCEYVYCBYVDK-UHFFFAOYSA-N (2-dimethylsilylphenyl)-dimethylsilane Chemical compound C[SiH](C)C1=CC=CC=C1[SiH](C)C QAUCEYVYCBYVDK-UHFFFAOYSA-N 0.000 description 2
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- ZWJPCOALBPMBIC-UHFFFAOYSA-N diphenylketene Chemical compound C=1C=CC=CC=1C(=C=O)C1=CC=CC=C1 ZWJPCOALBPMBIC-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 150000002391 heterocyclic compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 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
- -1 phenyltolyl ketene Chemical compound 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 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
- UCUFSUDAUWQDBI-UHFFFAOYSA-N (2-diethylsilylphenyl)-diethylsilane Chemical compound CC[SiH](CC)C1=CC=CC=C1[SiH](CC)CC UCUFSUDAUWQDBI-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- WXUPAJYKIZLYAE-UHFFFAOYSA-N 2-butylhex-1-en-1-one Chemical compound CCCCC(=C=O)CCCC WXUPAJYKIZLYAE-UHFFFAOYSA-N 0.000 description 1
- GFVFSRZJKWODDS-UHFFFAOYSA-N 2-phenylbut-1-en-1-one Chemical compound CCC(=C=O)C1=CC=CC=C1 GFVFSRZJKWODDS-UHFFFAOYSA-N 0.000 description 1
- DIWRARNGNXJDNM-UHFFFAOYSA-N C(C)C1=CC(=C(C=C1)[SiH](C)C)[SiH](C)C Chemical compound C(C)C1=CC(=C(C=C1)[SiH](C)C)[SiH](C)C DIWRARNGNXJDNM-UHFFFAOYSA-N 0.000 description 1
- VYNNIIPRNWHFHB-UHFFFAOYSA-N C(CC)[SiH](CCC)C1=C(C=CC=C1)[SiH](CCC)CCC Chemical compound C(CC)[SiH](CCC)C1=C(C=CC=C1)[SiH](CCC)CCC VYNNIIPRNWHFHB-UHFFFAOYSA-N 0.000 description 1
- JSBKSSDKCAEBOK-UHFFFAOYSA-N C[SiH](C1=C(C=CC=C1)[SiH](CC)CC)C Chemical compound C[SiH](C1=C(C=CC=C1)[SiH](CC)CC)C JSBKSSDKCAEBOK-UHFFFAOYSA-N 0.000 description 1
- FVWDOVCMNHXGTL-UHFFFAOYSA-N C[SiH](C1=C(C=CC=C1)[SiH](CCC)C)CCC Chemical compound C[SiH](C1=C(C=CC=C1)[SiH](CCC)C)CCC FVWDOVCMNHXGTL-UHFFFAOYSA-N 0.000 description 1
- WIUYVVKALHZPCA-UHFFFAOYSA-N ClC1=CC(=C(C=C1)[SiH](C)C)[SiH](C)C Chemical compound ClC1=CC(=C(C=C1)[SiH](C)C)[SiH](C)C WIUYVVKALHZPCA-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- WKUZQEWAZYLGEI-UHFFFAOYSA-N [Ni].C(=CC=CC)P(C=CC=CC)C=CC=CC.C(=CC=CC)P(C=CC=CC)C=CC=CC Chemical compound [Ni].C(=CC=CC)P(C=CC=CC)C=CC=CC.C(=CC=CC)P(C=CC=CC)C=CC=CC WKUZQEWAZYLGEI-UHFFFAOYSA-N 0.000 description 1
- PXCBSZFSOJWBGA-UHFFFAOYSA-N [Pt].C(CCC)P(CCCC)CCCC Chemical compound [Pt].C(CCC)P(CCCC)CCCC PXCBSZFSOJWBGA-UHFFFAOYSA-N 0.000 description 1
- IICWLQZAPBVDRP-UHFFFAOYSA-N [Pt].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C=CC Chemical compound [Pt].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C=CC IICWLQZAPBVDRP-UHFFFAOYSA-N 0.000 description 1
- GSTMGBYOYFWLFB-UHFFFAOYSA-N [Pt].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C=CCC Chemical compound [Pt].C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C=CCC GSTMGBYOYFWLFB-UHFFFAOYSA-N 0.000 description 1
- AOMCNAPFSXOLGH-UHFFFAOYSA-N [SiH3]c1ccccc1[SiH3] Chemical compound [SiH3]c1ccccc1[SiH3] AOMCNAPFSXOLGH-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 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
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JSEMCPMTAXQTJN-UHFFFAOYSA-N but-1-en-1-one Chemical compound CCC=C=O JSEMCPMTAXQTJN-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- 238000004587 chromatography analysis Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 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
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- HKVYMVXTDAHXIB-UHFFFAOYSA-N dimethyl(phenyl)phosphane platinum Chemical compound [Pt].CP(C1=CC=CC=C1)C HKVYMVXTDAHXIB-UHFFFAOYSA-N 0.000 description 1
- HASCQPSFPAKVEK-UHFFFAOYSA-N dimethyl(phenyl)phosphine Chemical compound CP(C)C1=CC=CC=C1 HASCQPSFPAKVEK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- WTJUVUFZLOWGLU-UHFFFAOYSA-N ethyl-[2-[ethyl(methyl)silyl]phenyl]-methylsilane Chemical compound C[SiH](C1=C(C=CC=C1)[SiH](CC)C)CC WTJUVUFZLOWGLU-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 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
- 239000012442 inert solvent Substances 0.000 description 1
- UJNZOIKQAUQOCN-UHFFFAOYSA-N methyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C)C1=CC=CC=C1 UJNZOIKQAUQOCN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- UYLRKRLDQUXYKB-UHFFFAOYSA-N nickel;triphenylphosphane Chemical compound [Ni].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 UYLRKRLDQUXYKB-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 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
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- UUEVFMOUBSLVJW-UHFFFAOYSA-N oxo-[[1-[2-[2-[2-[4-(oxoazaniumylmethylidene)pyridin-1-yl]ethoxy]ethoxy]ethyl]pyridin-4-ylidene]methyl]azanium;dibromide Chemical compound [Br-].[Br-].C1=CC(=C[NH+]=O)C=CN1CCOCCOCCN1C=CC(=C[NH+]=O)C=C1 UUEVFMOUBSLVJW-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- QJPQVXSHYBGQGM-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].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 QJPQVXSHYBGQGM-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- ZJAHNELKSLSUNS-UHFFFAOYSA-N platinum;tributylphosphane Chemical compound [Pt].CCCCP(CCCC)CCCC.CCCCP(CCCC)CCCC ZJAHNELKSLSUNS-UHFFFAOYSA-N 0.000 description 1
- FBCMODDAYVHEHB-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].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 FBCMODDAYVHEHB-UHFFFAOYSA-N 0.000 description 1
- SYKXNRFLNZUGAJ-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].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.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 SYKXNRFLNZUGAJ-UHFFFAOYSA-N 0.000 description 1
- XAKYZBMFCZISAU-UHFFFAOYSA-N platinum;triphenylphosphane Chemical compound [Pt].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 XAKYZBMFCZISAU-UHFFFAOYSA-N 0.000 description 1
- UYLUJGRCKKSWHS-UHFFFAOYSA-N prop-1-en-1-one Chemical compound CC=C=O UYLUJGRCKKSWHS-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- UKRDPEFKFJNXQM-UHFFFAOYSA-N vinylsilane Chemical group [SiH3]C=C UKRDPEFKFJNXQM-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、医薬、農薬等のファインケミカルズの合成中
間体として有用な2,1,4-ベンゾオキサジシラン誘導体及
びその製造方法に関するものである。TECHNICAL FIELD The present invention relates to a 2,1,4-benzoxadisilane derivative useful as a synthetic intermediate for fine chemicals such as pharmaceuticals and agricultural chemicals, and a method for producing the same.
従来の技術 ２個のケイ素原子と１個の窒素原子を構成員子として含
む複素環化合物としては、これまでベンゾアザジシリジ
ン誘導体が知られているだけで（「J.Organometal.Che
m.」第228巻、第301〜308頁）、2,1,4-ベンゾオキサジ
シラン構造をもつ化合物はまだ知られていない。このも
のはビニルシラン部分及びシリルエノールエーテル部分
を含むため医薬、農薬などの合成中間体として注目され
ている。PRIOR ART As a heterocyclic compound containing two silicon atoms and one nitrogen atom as constituent members, only a benzoazadisyridine derivative has been known so far (see “J.Organometal.Che”).
m. "228, 301-308), compounds having a 2,1,4-benzoxadisilane structure are not known yet. Since it contains a vinylsilane moiety and a silyl enol ether moiety, it is attracting attention as a synthetic intermediate for medicines, agricultural chemicals and the like.
発明が解決しようとする課題 本発明は、入手容易な原料を用いて、簡単な反応によ
り、２個のケイ素原子及び１個の酸素原子を構成員子と
するベンゼン縮合複素六員環化合物、特に新規化合物で
ある一般式 （式中のR1，R2，R3及びR4はそれぞれ同一又は異なった
低級アルキル基若しくは水素原子、R5は炭化水素基又は
水素原子、R6は炭化水素基である） で表わされる化合物を提供することを目的としてなされ
たものである。DISCLOSURE OF THE INVENTION The present invention is directed to a benzene-fused heterocyclic 6-membered ring compound having two silicon atoms and one oxygen atom as constituent members by a simple reaction using readily available raw materials, General formula that is a new compound (In the formula, R 1 , R 2 , R 3 and R 4 are the same or different lower alkyl groups or hydrogen atoms, R 5 is a hydrocarbon group or hydrogen atom, and R 6 is a hydrocarbon group) It was made for the purpose of providing a compound.
課題を解決するための手段 本発明者らは、ケイ素原子を構成員子とする複素環化合
物を製造する方法について、種々研究を重ねた結果、一
般式 （式中のR1，R2，R3及びR4は前記と同じ意味をもつ） で表わされる化合物と、一般式 （式中のR5及びR6は前記と同じ意味をもつ） で表わされるケテンとを、特定の触媒の存在下で反応さ
せると、前記一般式（Ｉ）で表わされる化合物が得られ
ることを見出し、これに基づき本発明を完成するに至っ
た。Means for Solving the Problems The present inventors have conducted various researches on a method for producing a heterocyclic compound having a silicon atom as a member, and as a result, (Wherein R 1 , R 2 , R 3 and R 4 have the same meanings as described above), and a compound of the general formula (Wherein R 5 and R 6 have the same meaning as described above) in the presence of a specific catalyst, a compound represented by the general formula (I) can be obtained. The present invention has been completed based on the heading.
すなわち、本発明は、前記一般式（II）で表わされる化
合物と、一般式（III）で表わされるケテンとを、白
金、パラジウム及びニッケルの中から選ばれた遷移金属
の、不飽和炭化水素及びホスフィン類の中から選ばれた
少なくとも１種の配位子を含む錯体の存在下で反応させ
る方法及びこの方法により得られる前記一般式（Ｉ）で
表わされる新規化合物を提供するものである。That is, the present invention provides a compound represented by the general formula (II) and a ketene represented by the general formula (III), an unsaturated hydrocarbon of a transition metal selected from platinum, palladium and nickel, and The present invention provides a method of reacting in the presence of a complex containing at least one ligand selected from phosphines, and a novel compound represented by the above general formula (I) obtained by this method.
本発明方法において、出発原料として用いられる一般式
（II）で表わされる化合物の中のR1，R2，R3及びR4はそ
れぞれメチル基、エチル基、プロピル基、ブチル基など
のアルキル基若しくは水素原子であって、これらは、い
ずれも同一であってもよいし、またたがいに異なってい
てもよい。また、この一般式（II）の中のベンゼン環
は、反応に対して不活性の置換基によって置換されてい
てもよい。したがって、一般式（II）の化合物の例とし
ては、o-ジシリルベンゼン、ｏ−ビス（ジメチルシリ
ル）ベンゼン、o-ビス（ジエチルシリル）ベンゼン、o-
ビス（ジプロピルシリル）ベンゼン、o-ビス（メチルエ
チルシリル）ベンゼン、o-ビス（メチルプロピルシリ
ル）ベンゼン、1-ジメチルシリル‐2-ジエチルシリルベ
ンゼン、1-メチル‐2,3-ビス（ジメチルシリル）ベンゼ
ン、1-エチル‐3,4-ビス（ジメチルシリル）ベンゼン、
1-クロル‐3,4-ビス（ジメチルシリル）ベンゼンなどが
挙げられる。In the method of the present invention, R 1 , R 2 , R 3 and R 4 in the compound represented by the general formula (II) used as a starting material are each an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group. Or hydrogen atoms, which may be the same or different from each other. Further, the benzene ring in the general formula (II) may be substituted with a substituent inert to the reaction. Therefore, examples of the compound of the general formula (II) include o-disilylbenzene, o-bis (dimethylsilyl) benzene, o-bis (diethylsilyl) benzene, o-
Bis (dipropylsilyl) benzene, o-bis (methylethylsilyl) benzene, o-bis (methylpropylsilyl) benzene, 1-dimethylsilyl-2-diethylsilylbenzene, 1-methyl-2,3-bis (dimethyl) Silyl) benzene, 1-ethyl-3,4-bis (dimethylsilyl) benzene,
Examples thereof include 1-chloro-3,4-bis (dimethylsilyl) benzene.
次に、この一般式（II）の化合物と反応させるケテンと
しては、一般式（III）中のR5及びR6がメチル基、エチ
ル基、プロピル基、ヘキシル基、オクチル基のようなア
ルキル基、シクロペンチル基、シクロヘキシル基のよう
なシクロアルキル基、ベンジル基のようなアラルキル
基、フェニル基、ナフチル基のようなアリール基などの
炭化水素基であるものやR5が水素原子でR6が前記の炭化
水素基であるものを挙げることができる。このようなケ
テンの例としては、メチルケテン、エチルケテン、ジブ
チルケテン、エチルフェニルケテン、ジフェニルケテ
ン、フェニルトリルケテン、ベンジルケテンなどがあ
る。Next, as the ketene reacted with the compound of the general formula (II), R 5 and R 6 in the general formula (III) are alkyl groups such as methyl group, ethyl group, propyl group, hexyl group and octyl group. , Cyclopentyl group, cycloalkyl group such as cyclohexyl group, aralkyl group such as benzyl group, phenyl group, hydrocarbon group such as aryl group such as naphthyl group, R 5 is a hydrogen atom and R 6 is And a hydrocarbon group of. Examples of such ketene include methyl ketene, ethyl ketene, dibutyl ketene, ethylphenyl ketene, diphenyl ketene, phenyltolyl ketene, benzyl ketene and the like.
本発明方法においては、一般式（II）で表わされる化合
物と一般式（III）で表わされるケテンとをモル比で1:1
0ないし10:1好ましくは1:2ないし2:1の範囲で用いられ
る。In the method of the present invention, the compound represented by the general formula (II) and the ketene represented by the general formula (III) are used in a molar ratio of 1: 1.
It is used in the range of 0 to 10: 1, preferably 1: 2 to 2: 1.
本発明方法においては、一般式（II）で表わされる化合
物と一般式（III）で表わされるケテンとの反応を、白
金、パラジウム及びニッケルの中から選ばれた遷移金属
の、不飽和炭化水素及びホスフィン類を配位子とした錯
体から成る触媒の存在下で行うことが必要である。この
不飽和炭化水素の配位子の例としては、エチレン、プロ
ペン、ブテンのようなオレフィンやジフェニルアセチレ
ン、フェニルアセチレンのようなアセチレン化合物を、
またホスフィン類の配位子としては、トリメチルホスフ
ィン、トリフェニルホスフィン、ジフェニルメチルホス
フィン、フェニルジメチルホスフィン、トリブチルホス
フィン、トリシクロヘキシルホスフィンなどをそれぞれ
挙げることができる。In the method of the present invention, the reaction between the compound represented by the general formula (II) and the ketene represented by the general formula (III) is carried out by using an unsaturated hydrocarbon of a transition metal selected from platinum, palladium and nickel. It is necessary to carry out in the presence of a catalyst composed of a complex having phosphines as a ligand. Examples of the unsaturated hydrocarbon ligand include olefins such as ethylene, propene and butene, and acetylene compounds such as diphenylacetylene and phenylacetylene.
Examples of phosphine ligands include trimethylphosphine, triphenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, tributylphosphine, and tricyclohexylphosphine.
また、本発明では、これらの錯体を単独でなく、２種以
上を共存させて実施してもよく、さらに錯体と共に該錯
体にふくまれるものと同一もしくは異なるホスフィン、
オレフィン又はアセチレン配位子を添加して実施するこ
とも本発明の有利な態様に含まれる。Further, in the present invention, these complexes may be carried out in the presence of not only one of them but also of two or more thereof, and the same or different phosphine as that included in the complex together with the complex,
It is also included in an advantageous embodiment of the present invention to carry out by adding an olefin or acetylene ligand.
したがって、この触媒として用いられる錯体の例として
は、（η‐エチレン）ビス（トリフェニルホスフィン）
白金、（η‐エチレン）ビス（トリフェニルホスフィ
ン）パラジウム、（η‐エチレン）ビス（トリフェニル
ホスフィン）ニッケル、（η‐エチレン）ビス（トリブ
チルホスフィン）白金、（η‐エチレン）ビス（トリシ
クロヘキシルホスフィン）パラジウム、（η‐エチレ
ン）ビス（トリペンタジエニルホスフィン）ニッケル、
（プロペン）ビス（トリフェニルホスフィン）白金、
（ブテン）ビス（トリフェニルホスフィン）白金、テト
ラキス（トリフェニルホスフィン）白金、ビス（η‐1,
5-シクロオクタジエン）白金、トリス（η‐エチレン）
白金、シクロロビス（フェニルジメチルホスフィン）白
金、クロロヒドリドビス（トリブチルホスフィン）白
金、ジクロロ（η‐1,5-シクロオクタジエン）白金、ジ
フェニルアセチレンビス（トリフェニルホスフィン）白
金などが挙げられる。Therefore, an example of a complex used as this catalyst is (η-ethylene) bis (triphenylphosphine)
Platinum, (η-ethylene) bis (triphenylphosphine) palladium, (η-ethylene) bis (triphenylphosphine) nickel, (η-ethylene) bis (tributylphosphine) platinum, (η-ethylene) bis (tricyclohexylphosphine) ) Palladium, (η-ethylene) bis (tripentadienylphosphine) nickel,
(Propene) bis (triphenylphosphine) platinum,
(Butene) bis (triphenylphosphine) platinum, tetrakis (triphenylphosphine) platinum, bis (η-1,
5-cyclooctadiene) platinum, tris (η-ethylene)
Platinum, cyclolobis (phenyldimethylphosphine) platinum, chlorohydridobis (tributylphosphine) platinum, dichloro (η-1,5-cyclooctadiene) platinum, diphenylacetylenebis (triphenylphosphine) platinum and the like can be mentioned.
これらの触媒の使用量としては、一般式（II）で表わさ
れる化合物１モル当り、0.00001〜0.5モルの範囲で選ば
れる。The amount of these catalysts used is selected in the range of 0.00001 to 0.5 mol per mol of the compound represented by the general formula (II).
本発明方法における一般式（II）で表わされる化合物と
一般式（III）で表わされるケテンとの反応は、次の反
応式に従って進行し、一般式（Ｉ）で表わされる2,1,4-
ベンゾオキサジシラン誘導体が生成する。In the method of the present invention, the reaction between the compound represented by the general formula (II) and the ketene represented by the general formula (III) proceeds according to the following reaction formula to give 2,1,4-
A benzoxadisilane derivative is produced.
（式中のR1，R2，R3，R4，R5及びR6は前記と同じ意味を
もつ） この反応は、溶媒を用いずに行うことができるが、必要
ならば反応の生起に障害とならない不活性溶媒中で行う
こともできる。このような溶媒は、使用される原料化合
物の反応性や沸点を考慮して選ばれるが、通常は、炭化
水素類やエーテル類の中から選ぶのが好ましい。 (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as described above.) This reaction can be carried out without using a solvent, but if necessary, the reaction may occur. It can also be carried out in an inert solvent that does not interfere with the above. Such a solvent is selected in consideration of the reactivity and boiling point of the raw material compound used, but normally, it is preferable to select it from hydrocarbons and ethers.
この反応は、０℃以下でも進行するが、反応速度を促進
するために250℃までの温度で加熱して行うのが好まし
い。一般的にいって、好適な温度範囲は０℃ないし150
℃の間である。This reaction proceeds even at 0 ° C. or lower, but it is preferable to carry out heating at a temperature up to 250 ° C. in order to accelerate the reaction rate. Generally speaking, the preferred temperature range is 0 ° C to 150 ° C.
Between ℃.
反応終了後、反応混合物から溶媒を除去し、慣用の分離
手段及び精製手段例えば精留、再結晶、クロマトグラフ
ィ等を用いて目的化合物を単離する。After completion of the reaction, the solvent is removed from the reaction mixture, and the desired compound is isolated by using conventional separation means and purification means such as rectification, recrystallization and chromatography.
得られた目的化合物の同定は、核磁気共鳴スペクトル、
赤外吸収スペクトル、元素分析値などによって行うこと
ができる。Identification of the obtained target compound, nuclear magnetic resonance spectrum,
It can be performed by infrared absorption spectrum, elemental analysis value and the like.
発明の効果 本発明によれば、容易に入手可能なo-ビス（ジアルキル
シリル）ベンゼンとケテンから簡単な方法で、新規な2,
1,4-ベンゾオキサジシラン誘導体を得ることができ、医
薬、農薬のための新らしい原料を提供しうる。EFFECTS OF THE INVENTION According to the present invention, a novel method for producing novel 2, -bis (dialkylsilyl) benzene and ketene by a simple method
It is possible to obtain a 1,4-benzoxadisilane derivative and provide a new raw material for medicines and agricultural chemicals.
実施例 次に実施例によって本発明をさらに詳細に説明する。EXAMPLES Next, the present invention will be described in more detail by way of examples.
実施例１ Pt（CH2＝CH2）(PPh3)2を0.005ミリモル及びo-ビス（ジ
メチルシリル）ベンゼンを0.25ミリモル含むベンゼン溶
液２ミリリットルに30℃にて、ジフェニルケテンを0.25
ミリモル含むベンゼン溶液２ミリリットルを加え、30℃
にて反応させた。１日間反応させた後濃縮し、蒸留する
ことにより、次式で示される1,1,4,4-テトラメチル‐3-
（ジフェニル）メチリデン‐2,1,4-ベンゾオキサジシラ
ンを40％の収率で得た。Example 1 2 ml of a benzene solution containing 0.005 mmol of Pt (CH 2 ═CH 2 ) (PPh 3 ) 2 and 0.25 mmol of o-bis (dimethylsilyl) benzene was added at 30 ° C. to 0.25 of diphenylketene.
Add 2 ml of benzene solution containing millimole, 30 ℃
It was made to react with. After reacting for 1 day, the mixture is concentrated and distilled to give 1,1,4,4-tetramethyl-3-
(Diphenyl) methylidene-2,1,4-benzoxadisilane was obtained in a yield of 40%.
この化合物は文献に未収載の新規化合物であり、その物
性値、スペクトルデータは以下の通りであった。1 H−NMR（CDCl3）：δ7.46−7.02（m,14H）,0.38（s,6
H）,0.01（s,6H） GC−MS（EI,70eV）:386（M+,96）,371（10）,193（10
0） 元素分析値：実測値 Ｃ 74.33％,H 6.69％ 理論値 Ｃ 74.56％,H 6.78％ このものの赤外吸収スペクトルを第１図に示す。 This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows. 1 H-NMR (CDCl 3 ): δ7.46-7.02 (m, 14H), 0.38 (s, 6
H), 0.01 (s, 6H) GC-MS (EI, 70eV): 386 (M + , 96), 371 (10), 193 (10
0) Elemental analysis value: measured value C 74.33%, H 6.69% theoretical value C 74.56%, H 6.78% The infrared absorption spectrum of this product is shown in FIG.
第１図は、本発明化合物の１例の赤外吸収スペクトル図
である。FIG. 1 is an infrared absorption spectrum diagram of an example of the compound of the present invention.
Claims (2)
アルキル基若しくは水素原子、R5は炭化水素基又は水素
原子、R6は炭化水素基である） で表わされる2,1,4-ベンゾオキサジシラン誘導体。1. A general formula (Wherein R 1 , R 2 , R 3 and R 4 are the same or different alkyl groups or hydrogen atoms, R 5 is a hydrocarbon group or a hydrogen atom, and R 6 is a hydrocarbon group) 1,1,4-Benzoxadisilane derivative.
アルキル基若しくは水素原子である） で表わされる化合物と、一般式 （式中のR5は炭化水素基又は水素原子、R6は炭化水素基
である） で表わされるケテンとを、白金、パラジウム及びニッケ
ルの中から選ばれた遷移金属の、不飽和炭化水素及びホ
スフィン類の中から選ばれた少なくとも１種の配位子を
含む錯体の存在下に反応させることを特徴とする、一般
式 （式中のR1，R2，R3，R4，R5及びR6は前記と同じ意味を
もつ） で表わされる2,1,4-ベンゾオキサジシラン誘導体の製造
方法。2. General formula (Wherein R 1 , R 2 , R 3 and R 4 are the same or different alkyl groups or hydrogen atoms) and a compound of the general formula (Wherein R 5 is a hydrocarbon group or a hydrogen atom, and R 6 is a hydrocarbon group) is a ketene represented by an unsaturated hydrocarbon of a transition metal selected from platinum, palladium and nickel. General formula characterized by reacting in the presence of a complex containing at least one ligand selected from phosphines (Wherein R 1 , R 2 , R 3 , R 4 , R 5 and R 6 have the same meanings as described above), and a method for producing a 2,1,4-benzoxadisilane derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2057277A JPH0730101B2 (en) | 1990-03-08 | 1990-03-08 | 2,1,4-benzoxadisilane derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2057277A JPH0730101B2 (en) | 1990-03-08 | 1990-03-08 | 2,1,4-benzoxadisilane derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258793A JPH03258793A (en) | 1991-11-19 |
| JPH0730101B2 true JPH0730101B2 (en) | 1995-04-05 |
Family
ID=13051045
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2057277A Expired - Lifetime JPH0730101B2 (en) | 1990-03-08 | 1990-03-08 | 2,1,4-benzoxadisilane derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730101B2 (en) |
-
1990
- 1990-03-08 JP JP2057277A patent/JPH0730101B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03258793A (en) | 1991-11-19 |
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