JP4391164B2 - 三次元かご状遷移金属錯体を用いる化学反応方法 - Google Patents
三次元かご状遷移金属錯体を用いる化学反応方法 Download PDFInfo
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- JP4391164B2 JP4391164B2 JP2003305772A JP2003305772A JP4391164B2 JP 4391164 B2 JP4391164 B2 JP 4391164B2 JP 2003305772 A JP2003305772 A JP 2003305772A JP 2003305772 A JP2003305772 A JP 2003305772A JP 4391164 B2 JP4391164 B2 JP 4391164B2
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- 238000006243 chemical reaction Methods 0.000 title claims description 30
- 238000000034 method Methods 0.000 title claims description 15
- 229910052723 transition metal Inorganic materials 0.000 title description 12
- 150000003624 transition metals Chemical class 0.000 title description 10
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims description 57
- 239000002904 solvent Substances 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 7
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 claims description 7
- 239000004914 cyclooctane Substances 0.000 claims description 7
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- CBMYFVSIIYILRH-UHFFFAOYSA-N 2,4,6-tri-4-pyridyl-1,3,5-triazine Chemical compound C1=NC=CC(C=2N=C(N=C(N=2)C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 CBMYFVSIIYILRH-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 12
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 11
- 150000002894 organic compounds Chemical class 0.000 description 8
- -1 hydrocarbons Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000007872 degassing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- FOWDOWQYRZXQDP-UHFFFAOYSA-N adamantan-2-ol Chemical compound C1C(C2)CC3CC1C(O)C2C3 FOWDOWQYRZXQDP-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- 238000001362 electron spin resonance spectrum Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000007539 photo-oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZMQLKBAJUGKDDO-UHFFFAOYSA-N 4-(3,5-dipyridin-4-ylphenyl)pyridine Chemical compound C1=NC=CC(C=2C=C(C=C(C=2)C=2C=CN=CC=2)C=2C=CN=CC=2)=C1 ZMQLKBAJUGKDDO-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000011908 [2 + 2] photodimerization Methods 0.000 description 1
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 description 1
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical class [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- QVGXLLKOCUKJST-NJFSPNSNSA-N oxygen-18 atom Chemical compound [18O] QVGXLLKOCUKJST-NJFSPNSNSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
2価のパラジウム錯体(en)Pd(NO3)2 (式中、enはエチレンジアミンを示す。)(1)と3座配位子2,4,6−トリス(4−ピリジル)−1,3,5−トリアジン(2)とを用いて、特開2000−086682号及び特開2000−086683号公報に記載の方法によって三次元かご状パラジウム錯体(3)を合成した。
水にアダマンタンとパラジウム錯体(en)Pd(NO3)2 を加え、これに実施例1と同様にして室温で30分間光照射したが、アダマンタンは何ら反応しなかった。
実施例1と同様にして合成したかご状パラジウム錯体5μmolを重水(D2O)1.0mLに100℃で溶解させ、得られた溶液にシクロオクタンの過剰量(約200μL)を加え、室温で10分間攪拌した。プロトン−NMRスペクトル(500MHz、溶媒D2O、外部標準TMS)の測定から、シクロオクタンは3〜4分子がかご状錯体に取り込まれていることが確認された。
Claims (4)
- 配位子として2,4,6−トリス(4−ピリジル)−1,3,5−トリアジンを有する三次元かご状パラジウム錯体に溶媒中で脂肪族環状炭化水素をゲスト分子として包接させて包接錯体とし、これに光照射し、上記錯体を励起して、上記脂肪族環状炭化水素に酸化反応させて、アルコール及び/又はケトンを生成させることを特徴とする化学反応方法。
- 脂肪族環状炭化水素がアダマンタン又はシクロオクタンである請求項1に記載の化学反応方法。
- アダマンタンに酸化反応させて、アダマンタノールを生成させる請求項1に記載の化学反応方法。
- シクロオクタンに酸化反応させて、シクロオクタノール及びシクロオクタノンを生成させる請求項1に記載の化学反応方法。
-
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JP2003305772A JP4391164B2 (ja) | 2003-08-29 | 2003-08-29 | 三次元かご状遷移金属錯体を用いる化学反応方法 |
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JP2003305772A JP4391164B2 (ja) | 2003-08-29 | 2003-08-29 | 三次元かご状遷移金属錯体を用いる化学反応方法 |
Publications (2)
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JP2005075751A JP2005075751A (ja) | 2005-03-24 |
JP4391164B2 true JP4391164B2 (ja) | 2009-12-24 |
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Families Citing this family (4)
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JP5149518B2 (ja) * | 2007-03-07 | 2013-02-20 | 国立大学法人 東京大学 | スピン性中空金属錯体及び有機ラジカル化合物の合成方法 |
US8791261B2 (en) | 2009-03-11 | 2014-07-29 | Japan Science And Technology Agency | Polyhedraltransition metal complex, transition metal complex containing ultrafine particles therein, and process for producing same |
JP6333527B2 (ja) | 2013-09-05 | 2018-05-30 | 国立大学法人北海道大学 | 有機elデバイス用薄膜及びその製造方法 |
CN103990494B (zh) * | 2014-05-20 | 2016-02-17 | 东华大学 | 一种非均相笼状金属配合物催化剂及其制备和应用 |
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