JPH0730100B2 - 5H-2,1,6-benzoxadisirocin derivative and method for producing the same - Google Patents
5H-2,1,6-benzoxadisirocin derivative and method for producing the sameInfo
- Publication number
- JPH0730100B2 JPH0730100B2 JP2057275A JP5727590A JPH0730100B2 JP H0730100 B2 JPH0730100 B2 JP H0730100B2 JP 2057275 A JP2057275 A JP 2057275A JP 5727590 A JP5727590 A JP 5727590A JP H0730100 B2 JPH0730100 B2 JP H0730100B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- group
- bis
- same
- benzene
- 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 4
- 150000001875 compounds Chemical class 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 150000002430 hydrocarbons Chemical group 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 150000003003 phosphines Chemical class 0.000 claims description 4
- 229930195735 unsaturated hydrocarbon Natural products 0.000 claims description 4
- 229930195733 hydrocarbon Chemical group 0.000 claims description 3
- 229910052759 nickel Inorganic materials 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
- 239000004215 Carbon black (E152) Chemical group 0.000 claims description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- 239000005977 Ethylene Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- -1 vinylcarbonyl compound Chemical class 0.000 description 6
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 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
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229920002554 vinyl polymer Polymers 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
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 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
- 239000003905 agrochemical Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 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 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 125000001424 substituent group Chemical group 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
- JLIDVCMBCGBIEY-UHFFFAOYSA-N 1-penten-3-one Chemical compound CCC(=O)C=C JLIDVCMBCGBIEY-UHFFFAOYSA-N 0.000 description 1
- KUIZKZHDMPERHR-UHFFFAOYSA-N 1-phenylprop-2-en-1-one Chemical compound C=CC(=O)C1=CC=CC=C1 KUIZKZHDMPERHR-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 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
- OBJMQJNDVNCCIN-UHFFFAOYSA-N C[SiH](C1=C(C(=CC=C1)C)[SiH](C)C)C Chemical compound C[SiH](C1=C(C(=CC=C1)C)[SiH](C)C)C OBJMQJNDVNCCIN-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
- 150000001299 aldehydes Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 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
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical group C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000012141 concentrate Substances 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
- 238000010586 diagram Methods 0.000 description 1
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 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
- 238000004821 distillation Methods 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
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 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
- 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
- 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
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-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
- DNAJDTIOMGISDS-UHFFFAOYSA-N prop-2-enylsilane Chemical group [SiH3]CC=C DNAJDTIOMGISDS-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
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 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
- 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、農薬等の合成中間体として有用な新規
化合物である5H-2,1,6-ベンゾオキサジシロシン誘導体
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 5H-2,1,6-benzoxadisylosin derivative which is a novel compound useful as a synthetic intermediate for medicines, agricultural chemicals and the like, and a method for producing the same. Is.
従来の技術 これまで、２個のケイ素原子と１個の酸素原子を構成員
子として含む複素８員環構造をもつ化合物は、全く知ら
れていない。2. Description of the Related Art Up to now, a compound having a hetero 8-membered ring structure containing two silicon atoms and one oxygen atom as members has not been known at all.
この２個のケイ素原子と１個の酸素原子を構成員子とし
て含む複素８員環例えば5H-2,1,6-オキサジシロシン
は、分子内にシリルエノールエーテル部分とアリルシラ
ン部分を有するので、各種合成中間体にシリル基やシロ
キシ基を導入する試薬としての利用が期待されていたに
もかかわらず、現在まで得られていなかった。This hetero 8-membered ring containing two silicon atoms and one oxygen atom as a member, for example, 5H-2,1,6-oxadisirocin, has a silyl enol ether moiety and an allyl silane moiety in the molecule, so Although it was expected to be used as a reagent for introducing a silyl group or siloxy group into an intermediate, it has not been obtained until now.
発明が解決しようとする課題 本発明は、シリル基とシロキシ基とが連結した形の複素
８員環をもつ新規な化合物を得ることを目的としてなさ
れたものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has been made for the purpose of obtaining a novel compound having a hetero 8-membered ring in which a silyl group and a siloxy group are linked.
課題を解決するための手段 本発明者らは、o-位に２個のシリル基を有するベンゼン
をビニルケトンのようなビニルカルボニル化合物と反応
させるとベンゼン環に縮合した、２個のケイ素及び１個
の酸素原子を含む複素８員環が形成されることを見出
し、この知見に基づいて本発明をなすに至った。すなわ
ち、本発明は、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
アルキル基若しくは水素原子であり、R5は水素原子又は
炭化水素基である） で表わされる5H-2,1,6-ベンゾオキサジシロシン誘導体
及びその製造方法を提供するものである。MEANS FOR SOLVING THE PROBLEMS The inventors of the present invention have proposed that when benzene having two silyl groups at the o-position is reacted with a vinylcarbonyl compound such as vinyl ketone, two silicon and one fused to a benzene ring are condensed. It was found that a hetero 8-membered ring containing the above oxygen atom was formed, and the present invention was completed based on this finding. That is, the present invention has the general formula (Wherein R 1 , R 2 , R 3 and R 4 are the same or different alkyl groups or hydrogen atoms, and R 5 is a hydrogen atom or a hydrocarbon group) 5H-2,1, The present invention provides a 6-benzooxadisirocin derivative and a method for producing the same.
本発明の化合物の例としては、前記一般式（Ｉ）におい
て、R1，R2，R3及びR4がすべて水素原子のもの、その一
部若しくは全部が、メチル基、エチル基、プロピル基、
ブチル基、ペンチル基、ヘキシル基のようなアルキル基
であるものを挙げることができる。これらの基はすべて
が同一であってもよいし、またその一部が同一であって
もよい。またR5の基はビニルケトンから誘導される残基
であって、この例としては、メチル基、エチル基、プロ
ピル基、ブチル基、ヘキシル基、オクチル基、デシル基
のようなアルキル基、フェニル基、o-、m-,p-トリル基
のようなアリール基、ベンジル基のようなアラルキル基
などの炭化水素基を挙げることができる。Examples of the compound of the present invention include those in which, in the general formula (I), R 1 , R 2 , R 3 and R 4 are all hydrogen atoms, part or all of which is a methyl group, an ethyl group or a propyl group. ,
Examples thereof include alkyl groups such as a butyl group, a pentyl group and a hexyl group. All of these groups may be the same or some of them may be the same. The group of R 5 is a residue derived from vinyl ketone, examples of which include a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, an alkyl group such as a decyl group, and a phenyl group. , Hydrocarbon groups such as aryl groups such as o-, m-, p-tolyl groups and aralkyl groups such as benzyl groups.
また、本発明の化合物中のベンゼン環には、ハロゲン原
子、アルキル基、アルコキシ基、ジアルキルアミノ基な
どの置換基を有することもできる。In addition, the benzene ring in the compound of the present invention may have a substituent such as a halogen atom, an alkyl group, an alkoxy group and a dialkylamino group.
これらの化合物は、いずれも文献に未収載の新規化合物
である。All of these compounds are new compounds not listed in the literature.
前記一般式（Ｉ）の化合物は、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
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である） で表わされるビニルカルボニル化合物を、白金、パラジ
ウム、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て含む錯体の存在
下で反応させることによって製造することができる。The compound of the general formula (I) has the 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) is used as a ligand for an unsaturated hydrocarbon and phosphines of a transition metal selected from platinum, palladium and nickel. Can be produced by reacting in the presence of a complex containing
この方法において、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 this method, 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 These are 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 compounds of general formula (II) are 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-diethylsilyl Benzene, 1-methyl-2,3-bis (dimethylsilyl) benzene,
Examples thereof include 1-ethyl-3,4-bis (dimethylsilyl) benzene and 1-chloro-3,4-bis (dimethylsilyl) benzene.
次に、この一般式（II）で表わされる化合物と反応させ
るビニル化合物のうち、一般式（III）中のR5が水素原
子の場合はアルデヒドすなわちプロペナールであり、R5
が炭化水素基の場合はビニルケトンである。このような
ビニルケトンの例としては、3-ブテン‐2-オン、4-ペン
テン‐3-オン、1-フェニル‐2-プロペン‐1-オンなどを
挙げることができる。Next, among the vinyl compounds reacted with the compound represented by the general formula (II), when R 5 in the general formula (III) is a hydrogen atom, it is an aldehyde, that is, propenal, and R 5
When is a hydrocarbon group, it is vinyl ketone. Examples of such vinyl ketones include 3-buten-2-one, 4-penten-3-one, 1-phenyl-2-propen-1-one and the like.
このビニル化合物は、一般式（II）で表わされる化合物
に対し、10:1ないし1:10、好ましくは2:1ないし1:2の範
囲のモル比で用いられる。This vinyl compound is used in a molar ratio of 10: 1 to 1:10, preferably 2: 1 to 1: 2, with respect to the compound represented by the general formula (II).
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）で表わされるビニル化合物との反応
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の中から選
ばれた少なくとも１種の配位子を含む錯体から成る触媒
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フェニルアセチレン、ジフェニルア
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 vinyl compound 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 containing at least one ligand selected from phosphines and phosphines. Examples of the unsaturated hydrocarbon ligands include olefins such as ethylene, propene and butene, and acetylene compounds such as phenylacetylene and diphenylacetylene, and phosphine ligands such as trimethylphosphine and triphenylphosphine. Examples thereof include phenylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, tributylphosphine and tricyclohexyphosphine.
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、さらに錯体と共に核錯
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 two or more kinds, not alone, and the same or different phosphine as that included in the nuclear 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、ジクロロビス（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)
Examples thereof include platinum, dichlorobis (phenyldimethylphosphine) platinum, chlorohydridobis (tributylphosphine) platinum, dichloro (η-1,5-cyclooctadiene) platinum, and diphenylacetylenebis (triphenylphosphine) platinum.
これらの触媒の使用量としては、一般式（II）で表わさ
れるo-ビス（ジアルキルシリル）ベンゼン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 1 mol of o-bis (dialkylsilyl) benzene represented by the general formula (II),
It is selected in the range of 0.00001 to 0.5 mol.
本発明方法における一般式（II）で表わされるo-ビス
（ジアルキルシリル）ベンゼンと一般式（III）で表わ
されるビニル化合物との反応は、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。The reaction of the o-bis (dialkylsilyl) benzene represented by the general formula (II) with the vinyl compound represented by the general formula (III) in the method of the present invention can be carried out without using a solvent, but if necessary, It can also be carried out in an inert solvent that does not hinder the occurrence of the reaction. Such solvents are
It is selected in consideration of the reactivity and boiling point of the raw material compound used, but it is usually 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精製する。After completion of the reaction, the solvent is removed from the reaction mixture, and the target compound is isolated and purified by using a conventional separation means and purification means such as rectification, recrystallization, chromatography and the like.
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等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 or the like.
発明の効果 本発明によれば、容易に入手しうるo-ビス（ジアルキル
シリル）ベンゼン、ビニルケトンのような原料化合物を
用いて、新規な5H-2,1,6-ベンゾオキサジシロシン誘導
体を製造することができ、医薬、農薬等のための新らし
い原料を提供することができる。EFFECTS OF THE INVENTION According to the present invention, a novel 5H-2,1,6-benzoxadisylosin derivative is produced by using readily available raw material compounds such as o-bis (dialkylsilyl) benzene and vinyl ketone. It is possible to provide new raw materials for medicines, agricultural chemicals and the like.
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40℃にて、3-ブテン‐2-オンを0.25
ミリモル含むベンゼン溶液２ミリリットルを加え、40℃
にて撹拌し、反応させた。２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、1,1,6,6-テトラメ
チル‐3-メチル‐5H-2,1,6-ベンゾオキサジシロシンを
収率88％で得た。Example 1 2 -Butene-2-one was added to 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 at 40 ° C. 0.25
Add 2 ml of benzene solution containing millimolar, 40 ℃
The mixture was stirred and reacted. After reacting for 2 days, concentrate and
Distillation gave 1,1,6,6-tetramethyl-3-methyl-5-methyl-5H-2,1,6-benzoxadisilocin represented by the following formula in a yield of 88%.
本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。 This compound was a novel compound not listed in the literature, and its physical properties and spectral data were as follows.
沸点65℃/0.5mmHg（クーゲルロール）1 H−NMR（CDCl3）：δ7.67−7.31（m,4H）,4.70（dd,J
＝6.1Hz,1H）,1.72（d,J＝1Hz,3H）,1.51（dd,J＝6.1H
z,1H）,0.46（s,6H）,0.31（s,6H）13 C−NMR（CDCl3）：δ146.81,146.04,143.44,134.90,1
33.85,128.67,127.97,103.89,22.13,14.75,1.30（2C）,
0.35（2C） GC−MS（EI,70eV）:262（M+,45）,247（８）,194（10
0） また、このものの赤外吸収スペクトルを第１図に示す。Boiling point 65 ° C / 0.5 mmHg (Kugelroll) 1 H-NMR (CDCl 3 ): δ7.67-7.31 (m, 4H), 4.70 (dd, J
= 6.1Hz, 1H), 1.72 (d, J = 1Hz, 3H), 1.51 (dd, J = 6.1H)
z, 1H), 0.46 (s, 6H), 0.31 (s, 6H) 13 C-NMR (CDCl 3 ): δ146.81,146.04,143.44,134.90,1
33.85,128.67,127.97,103.89,22.13,14.75,1.30 (2C),
0.35 (2C) GC-MS (EI, 70eV): 262 (M + , 45), 247 (8), 194 (10
0) 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であり、R5は水素原子又は
炭化水素基である） で表わされる5H-2,1,6-ベンゾオキサジシロシン誘導
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, and R 5 is a hydrogen atom or a hydrocarbon group) 5H-2,1, 6-benzoxadisirocin 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である） で表わされるビニルカルボニル化合物を、白金、パラジ
ウム、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
個の配位子を含む錯体の存在下で反応させることを特徴
とする、一般式 （式中のR1，R2，R3，R4及びR5は前記と同じ意味をも
つ） で表わされる5H-2,1,6-ベンゾオキサジシロシン誘導体
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) is selected from among unsaturated hydrocarbons and phosphines of a transition metal selected from platinum, palladium and nickel. At least 1
General formula characterized by reacting in the presence of a complex containing one ligand (Wherein R 1 , R 2 , R 3 , R 4 and R 5 have the same meanings as described above), and a method for producing a 5H-2,1,6-benzoxadisylosin derivative.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2057275A JPH0730100B2 (en) | 1990-03-08 | 1990-03-08 | 5H-2,1,6-benzoxadisirocin derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2057275A JPH0730100B2 (en) | 1990-03-08 | 1990-03-08 | 5H-2,1,6-benzoxadisirocin derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03258791A JPH03258791A (en) | 1991-11-19 |
| JPH0730100B2 true JPH0730100B2 (en) | 1995-04-05 |
Family
ID=13050986
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2057275A Expired - Lifetime JPH0730100B2 (en) | 1990-03-08 | 1990-03-08 | 5H-2,1,6-benzoxadisirocin derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0730100B2 (en) |
-
1990
- 1990-03-08 JP JP2057275A patent/JPH0730100B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03258791A (en) | 1991-11-19 |
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