JP2005187380A - Method for producing ruthenium carbene complex - Google Patents
Method for producing ruthenium carbene complex Download PDFInfo
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- JP2005187380A JP2005187380A JP2003429594A JP2003429594A JP2005187380A JP 2005187380 A JP2005187380 A JP 2005187380A JP 2003429594 A JP2003429594 A JP 2003429594A JP 2003429594 A JP2003429594 A JP 2003429594A JP 2005187380 A JP2005187380 A JP 2005187380A
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- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 35
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- -1 phosphine compound Chemical class 0.000 claims abstract description 40
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 16
- 239000012327 Ruthenium complex Substances 0.000 claims abstract description 15
- 125000005843 halogen group Chemical group 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 11
- 125000002723 alicyclic group Chemical group 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- WLPUWLXVBWGYMZ-UHFFFAOYSA-N tricyclohexylphosphine Chemical compound C1CCCCC1P(C1CCCCC1)C1CCCCC1 WLPUWLXVBWGYMZ-UHFFFAOYSA-N 0.000 claims description 9
- 125000001424 substituent group Chemical group 0.000 claims description 8
- CAHQGWAXKLQREW-UHFFFAOYSA-N Benzal chloride Chemical compound ClC(Cl)C1=CC=CC=C1 CAHQGWAXKLQREW-UHFFFAOYSA-N 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- WIWBLJMBLGWSIN-UHFFFAOYSA-L dichlorotris(triphenylphosphine)ruthenium(ii) Chemical compound [Cl-].[Cl-].[Ru+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.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 WIWBLJMBLGWSIN-UHFFFAOYSA-L 0.000 claims description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- FEWDXGMBVQULLN-UHFFFAOYSA-N 1-hydroxy-2-phenyl-1,5,6,7-tetrahydro-4H-benzimidazol-4-one Chemical compound ON1C=2CCCC(=O)C=2N=C1C1=CC=CC=C1 FEWDXGMBVQULLN-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- DHWBYAACHDUFAT-UHFFFAOYSA-N tricyclopentylphosphane Chemical compound C1CCCC1P(C1CCCC1)C1CCCC1 DHWBYAACHDUFAT-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 9
- 238000005649 metathesis reaction Methods 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- HPCDQQZOBUGTMG-UHFFFAOYSA-N [Ru]=Cc1ccccc1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 Chemical compound [Ru]=Cc1ccccc1.C1CCC(CC1)P(C1CCCCC1)C1CCCCC1 HPCDQQZOBUGTMG-UHFFFAOYSA-N 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 125000003944 tolyl group Chemical group 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- JIXOCHSERUXVMW-UHFFFAOYSA-M chlororuthenium Chemical compound [Ru]Cl JIXOCHSERUXVMW-UHFFFAOYSA-M 0.000 description 2
- 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 2
- VZXMCMGRKFXJJA-UHFFFAOYSA-N cycloocta-1,3-diene cycloocta-1,3,5-triene ruthenium Chemical compound [Ru].C1CCC=CC=CC1.C1CC=CC=CC=C1 VZXMCMGRKFXJJA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 239000003446 ligand Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VIHDTGHDWPVSMM-UHFFFAOYSA-N ruthenium;triphenylphosphane Chemical compound [Ru].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VIHDTGHDWPVSMM-UHFFFAOYSA-N 0.000 description 2
- XNBYBQSCHAFTIY-UHFFFAOYSA-N ruthenium;tris(2-methylphenyl)phosphane Chemical compound [Ru].CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C XNBYBQSCHAFTIY-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- QSSAZDNARJWYEF-UHFFFAOYSA-N 1-(dibromomethyl)-2-methylbenzene Chemical group CC1=CC=CC=C1C(Br)Br QSSAZDNARJWYEF-UHFFFAOYSA-N 0.000 description 1
- WPZKRYLMVCPDJR-UHFFFAOYSA-N 1-(dichloromethyl)-2-methylbenzene Chemical group CC1=CC=CC=C1C(Cl)Cl WPZKRYLMVCPDJR-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 238000006418 Brown reaction Methods 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003849 aromatic solvent Substances 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
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([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
- 150000008049 diazo compounds Chemical class 0.000 description 1
- CRGRWBQSZSQVIE-UHFFFAOYSA-N diazomethylbenzene Chemical compound [N-]=[N+]=CC1=CC=CC=C1 CRGRWBQSZSQVIE-UHFFFAOYSA-N 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000706 filtrate Substances 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
- 239000011261 inert gas Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- ZJQLZZWVCYKIJB-UHFFFAOYSA-N methylbenzene;ruthenium Chemical compound [Ru].[CH]C1=CC=CC=C1 ZJQLZZWVCYKIJB-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 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
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000006798 ring closing metathesis reaction 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
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical group C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- MPULMSAVZAPUQG-UHFFFAOYSA-N tri(cyclooctyl)phosphane Chemical compound C1CCCCCCC1P(C1CCCCCCC1)C1CCCCCCC1 MPULMSAVZAPUQG-UHFFFAOYSA-N 0.000 description 1
- MBFBOWOPHAIFBS-UHFFFAOYSA-N tri(hexan-2-yl)phosphane Chemical compound CCCCC(C)P(C(C)CCCC)C(C)CCCC MBFBOWOPHAIFBS-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 1
- IGNTWNVBGLNYDV-UHFFFAOYSA-N triisopropylphosphine Chemical compound CC(C)P(C(C)C)C(C)C IGNTWNVBGLNYDV-UHFFFAOYSA-N 0.000 description 1
- COIOYMYWGDAQPM-UHFFFAOYSA-N tris(2-methylphenyl)phosphane Chemical compound CC1=CC=CC=C1P(C=1C(=CC=CC=1)C)C1=CC=CC=C1C COIOYMYWGDAQPM-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
本発明は、ルテニウムカルベン錯体の製造方法に関する。特に、このルテニウムカルベン錯体を安価かつ安全に製造し得る方法に関する。 The present invention relates to a method for producing a ruthenium carbene complex. In particular, the present invention relates to a method capable of producing the ruthenium carbene complex inexpensively and safely.
ルテニウムカルベン錯体は、オレフィン化合物のメタセシス反応の触媒として知られ、最近、各種の有機化合物の合成あるいは重合体の製造に応用されるようになってきた。
従来からオレフィン化合物のメタセシス反応の触媒として、モリブデンまたはタングステン化合物を触媒とし、助触媒（活性化剤ともいう）としてアルキルアルミニウムを組み合わせた触媒系が使われている。しかし、この触媒系は水や空気に不安定で失活し易いため取り扱い難く、またオレフィン化合物に置換する官能基の種類によっても失活する場合があり適用が限定されていた。
１９９３年、新規なルテニウム錯体としてルテニウムカルベン錯体が開発された（非特許文献１参照）。その後の研究で、メタセシス反応活性を有し、従来のメタセシス反応触媒に比べて水や空気に安定であり、しかもオレフィン化合物に置換している官能基の影響を受け難いことが分かり、ジオレフィン化合物の閉環メタセシス反応による医薬品中間体の合成、環状オレフィン化合物のメタセシス重合によるポリマーの合成に応用されるようになってきた。
ルテニウムカルベン錯体として、カルベン部分及び配位子の構造が異なる種々の錯体が合成されているが、その典型的な錯体は次式（V）で表されるルテニウムカルベン錯体である。
Ruthenium carbene complexes are known as catalysts for metathesis reactions of olefin compounds, and have recently been applied to the synthesis of various organic compounds or the production of polymers.
Conventionally, as a catalyst for the metathesis reaction of an olefin compound, a catalyst system in which molybdenum or a tungsten compound is used as a catalyst and alkylaluminum is combined as a promoter (also referred to as an activator) has been used. However, since this catalyst system is unstable to water and air and easily deactivated, it is difficult to handle, and depending on the type of functional group substituted for the olefin compound, it may be deactivated and its application is limited.
In 1993, a ruthenium carbene complex was developed as a new ruthenium complex (see Non-Patent Document 1). Subsequent research shows that it has metathesis reaction activity, is more stable in water and air than conventional metathesis reaction catalysts, and is less susceptible to the functional groups substituted by olefin compounds. It has come to be applied to the synthesis of pharmaceutical intermediates by the ring-closing metathesis reaction and the synthesis of polymers by the metathesis polymerization of cyclic olefin compounds.
As the ruthenium carbene complex, various complexes having different carbene moieties and ligand structures have been synthesized. A typical complex is a ruthenium carbene complex represented by the following formula (V).
上記式（V）で表されるルテニウムカルベン錯体の合成法として、次のような方法が報告されている。
J.Am.Chem.Soc.,1996,118,p100（非特許文献２）には、ジクロロトリス（トリフェニルホスフィン）ルテニウムに、フェニルジアゾメタンを反応させ次いでトリシクロヘキシルホスフィンを加えて配位子交換させてジクロロビス（トリシクロヘキシルホスフィン）ベンジリデンルテニウムを得る方法が記載されている。
しかし、上記の方法は、爆発の危険性のあるジアゾ化合物を用いるため安全性に問題があり、希薄で、極低温の反応条件で合成せねばならずコストの高い合成方法となっている。
Organometallics,16,p4001 (1997)（非特許文献３）には、（シクロオクタジエン）（シクロオクタトリエン）ルテニウムに、塩化ベンザル及びトリシクロヘキシルホスフィンを反応させてジクロロビス（トリシクロヘキシルホスフィン）ベンジリデンルテニウムを得る方法が記載されている。しかし、この方法は、原料である（シクロオクタジエン）（シクロオクタトリエン）ルテニウムの合成が難しいため、コストの高い合成方法となっている。
特開２０００−７２７８８号公報（特許文献１）には、ジ-μ-クロロビス[(p-シメン)クロロルテニウム]に、塩化ベンザル、トリシクロヘキシルホスフィン及び亜鉛粉末を加えて反応させ、ジクロロビス（トリシクロヘキシルホスフィン）ベンジリデンルテニウムを得る方法が記載されている。
しかし、上記の方法は、原料であるジ-μ-クロロビス[(p-シメン)クロロルテニウム]は分子内に貴金属であるルテニウム原子を２個有する錯体であるが、２個のルテニウム原子のうち１個だけが目的のルテニウムカルベン錯体を生成するにすぎず、高コストな合成になっている。
The following method has been reported as a synthesis method of the ruthenium carbene complex represented by the above formula (V).
In J. Am. Chem. Soc., 1996, 118, p100 (Non-patent Document 2), dichlorotris (triphenylphosphine) ruthenium is reacted with phenyldiazomethane, followed by addition of tricyclohexylphosphine for ligand exchange. A process for obtaining dichlorobis (tricyclohexylphosphine) benzylidene ruthenium is described.
However, the above method has a problem in safety because it uses a diazo compound having a risk of explosion, and is a low cost synthesis method that must be synthesized under reaction conditions at a very low temperature.
Organometallics, 16, p4001 (1997) (Non-patent Document 3), (cyclooctadiene) (cyclooctatriene) ruthenium is reacted with benzal chloride and tricyclohexylphosphine to obtain dichlorobis (tricyclohexylphosphine) benzylidene ruthenium. A method is described. However, this method is a costly synthesis method because it is difficult to synthesize (cyclooctadiene) (cyclooctatriene) ruthenium as a raw material.
In JP-A-2000-72788 (Patent Document 1), dichlorobis (tricyclohexyl) is reacted by adding benzal chloride, tricyclohexylphosphine and zinc powder to di-μ-chlorobis [(p-cymene) chlororuthenium]. A process for obtaining phosphine) benzylidene ruthenium is described.
However, in the above method, the raw material di-μ-chlorobis [(p-cymene) chlororuthenium] is a complex having two ruthenium atoms which are noble metals in the molecule, but one of the two ruthenium atoms. Only one produces the desired ruthenium carbene complex, resulting in a costly synthesis.
本発明は、メタセシス反応の触媒として有用なルテニウムカルベン錯体を、安価な原料を用いて安全、かつ、効率良く製造して、工業的に使用可能な価格のルテニウムカルベン錯体の製造方法を提供するものである。 The present invention provides a method for producing a ruthenium carbene complex that is useful as a catalyst for a metathesis reaction by producing a ruthenium carbene complex that is safe and efficient using inexpensive raw materials and that can be used industrially. It is.
請求項１に記載の発明は、一般式（I）で表されるルテニウム錯体、一般式(II)で表されるホスフィン化合物、及び一般式(III)で表されるハロゲノ化合物を還元性金属の存在下に反応させることを特徴とする一般式(IV)で表されるルテニウムカルベン錯体の製造方法である。 According to the first aspect of the present invention, a ruthenium complex represented by the general formula (I), a phosphine compound represented by the general formula (II), and a halogeno compound represented by the general formula (III) are reduced with a reducing metal. This is a method for producing a ruthenium carbene complex represented by the general formula (IV), characterized by reacting in the presence.
請求項２に記載の発明は、上記一般式（I）で表されるルテニウム錯体１モルに対して一般式（II）で表されるホスフィン化合物を２モル以上、一般式（III）で表されるハロゲノ化合物を２モル以上、及び還元性金属を２グラム当量以上の割合で用いる請求項１に記載のルテニウムカルベン錯体の製造方法である。
請求項３に記載の発明は、一般式（I）で表されるルテニウム錯体が、ジクロロトリス（トリフェニルホスフィン）ルテニウムである請求項１又は請求項２に記載のルテニウムカルベン錯体の製造方法である。
請求項４に記載の発明は、一般式（II）で表されるホスフィン化合物が、トリシクロペンチルホスフィン又はトリシクロヘキシルホスフィンである請求項１ないし請求項３のいずれかに記載のルテニウムカルベン錯体の製造方法である。
請求項５に記載の発明は、一般式（III）で表されるハロゲノ化合物が、塩化ベンザル又は臭化ベンザルである請求項１ないし請求項４のいずれかに記載のルテニウムカルベン錯体の製造方法である。
請求項６に記載の発明は、還元性金属が、マグネシウム又は亜鉛である請求項１ないし請求項５のいずれかに記載のルテニウムカルベン錯体の製造方法である。
The invention according to claim 2 is represented by the general formula (III) in which at least 2 moles of the phosphine compound represented by the general formula (II) are represented by 1 mole of the ruthenium complex represented by the general formula (I). The method for producing a ruthenium carbene complex according to claim 1, wherein the halogeno compound is used in an amount of 2 mol or more and the reducing metal is used in a proportion of 2 gram equivalent or more.
Invention of Claim 3 is a manufacturing method of the ruthenium carbene complex of Claim 1 or Claim 2 whose ruthenium complex represented by general formula (I) is dichlorotris (triphenylphosphine) ruthenium. .
The invention according to claim 4 is the method for producing a ruthenium carbene complex according to any one of claims 1 to 3, wherein the phosphine compound represented by the general formula (II) is tricyclopentylphosphine or tricyclohexylphosphine. It is.
The invention according to claim 5 is the method for producing a ruthenium carbene complex according to any one of claims 1 to 4, wherein the halogeno compound represented by the general formula (III) is benzal chloride or benzal bromide. is there.
The invention according to claim 6 is the method for producing a ruthenium carbene complex according to any one of claims 1 to 5, wherein the reducing metal is magnesium or zinc.
本発明によって、メタセシス反応の触媒として有用なルテニウムカルベン錯体を、安価な原料を用いて安全、かつ、効率良く製造して、工業的に使用可能な価格のルテニウムカルベン錯体を製造し得る。 According to the present invention, a ruthenium carbene complex useful as a catalyst for a metathesis reaction can be produced safely and efficiently using an inexpensive raw material to produce a ruthenium carbene complex at an industrially usable price.
本発明のルテニウム錯体は、上記一般式（I）で表されるものを原料として製造される。上記一般式（I）中、Ｘ１はハロゲン原子を示し、Ｒ１は置換基を有してもよい芳香族炭化水素基を示す。
一般式（I）中のＸ１であるハロゲン原子としては、塩素、臭素、ヨウ素が挙げられ、その中でも入手の容易性から塩素が好ましい。
また、一般式（I）中のＲ１である置換基を有してもよい芳香族炭化水素基としては、フェニル基、トリル基、メシチル基などが挙げられ、その中でも入手の容易性からフェニル基、トリル基が好ましい。
The ruthenium complex of the present invention is produced using a material represented by the above general formula (I) as a raw material. In the general formula (I), X 1 represents a halogen atom, and R 1 represents an aromatic hydrocarbon group which may have a substituent.
Examples of the halogen atom that is X 1 in the general formula (I) include chlorine, bromine, and iodine. Among these, chlorine is preferable because of its availability.
In addition, examples of the aromatic hydrocarbon group which may have a substituent as R 1 in the general formula (I) include a phenyl group, a tolyl group, and a mesityl group. Group and tolyl group are preferable.
本発明で用いる一般式（I）で表されるルテニウム錯体としては、例えば、ジクロロトリス（トリフェニルホスフィン）ルテニウム、ジブロモトリス（トリフェニルホスフィン）ルテニウム、ジヨードトリス（トリフェニルホスフィン）ルテニウム、ジクロロトリス（トリトリルホスフィン）ルテニウム、ジブロモトリス（トリトリルホスフィン）ルテニウム、ジヨードトリス（トリトリルホスフィン）ルテニウム、ジクロロトリス（トリメシチルホスフィン）ルテニウム、ジブロモトリス（トリメシチルホスフィン）ルテニウム、ジヨードトリス（トリメシチルホスフィン）ルテニウムなどが挙げられる。その中でも、ジクロロトリス（トリフェニルホスフィン）ルテニウムが製造の容易性、入手の容易性の点で好ましいルテニウム錯体である。 Examples of the ruthenium complex represented by the general formula (I) used in the present invention include dichlorotris (triphenylphosphine) ruthenium, dibromotris (triphenylphosphine) ruthenium, diiodotris (triphenylphosphine) ruthenium, dichlorotris (tri Tolylphosphine) ruthenium, dibromotris (tritolylphosphine) ruthenium, diiodotris (tritolylphosphine) ruthenium, dichlorotris (trimesitylphosphine) ruthenium, dibromotris (trimesitylphosphine) ruthenium, diiodotris (trimesitylphosphine) ruthenium It is done. Among these, dichlorotris (triphenylphosphine) ruthenium is a preferable ruthenium complex from the viewpoint of ease of production and availability.
上記に好ましいルテニウム錯体として例示したジクロロトリス（トリフェニルホスフィン）ルテニウムは、例えば、新実験化学講座第１２巻有機金属化学（丸善、昭和５１年３月）p１６３に記載されている方法で製造することができる。 Dichlorotris (triphenylphosphine) ruthenium exemplified as a preferable ruthenium complex is manufactured by, for example, the method described in New Experimental Chemistry Course Vol. 12 Organometallic Chemistry (Maruzen, March 1976) p163. Can do.
本発明で用いるホスフィン化合物は、上記一般式（II）で表されるものであり、上記一般式（II）中、Ｒ２は炭素数２〜８の脂肪族炭化水素基または炭素数５〜８の脂環式炭化水素基を示す。
炭素数２〜８の脂肪族炭化水素基としては、エチル基、プロピル基、イソプロピル基、ブチル基、ブタン-２-イル基、ペンチル基、ヘキシル基、ヘキサン-２-イル基、ヘプチル基、オクタン-２-イル基などが挙げられる。また、炭素数５〜８の脂環式炭化水素基としては、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基が挙げられる。
The phosphine compound used in the present invention is represented by the above general formula (II). In the above general formula (II), R 2 is an aliphatic hydrocarbon group having 2 to 8 carbon atoms or 5 to 8 carbon atoms. Represents an alicyclic hydrocarbon group.
Examples of the aliphatic hydrocarbon group having 2 to 8 carbon atoms include ethyl group, propyl group, isopropyl group, butyl group, butan-2-yl group, pentyl group, hexyl group, hexane-2-yl group, heptyl group, and octane. -2-yl group and the like can be mentioned. Moreover, as a C5-C8 alicyclic hydrocarbon group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are mentioned.
本発明で用いる上記一般式（II）で表されるホスフィン化合物としては、例えば、トリイソプロピルホスフィン、トリブチルホスフィン、トリ（ヘキサン-２-イル）ホスフィン、トリシクロペンチルホスフィン、トリシクロヘキシルホスフィン、トリシクロオクチルホスフィンなどが挙げられる。その中でも、トリシクロペンチルホスフィン、トリシクロヘキシルホスフィンが最終的に得られるルテニウムカルベン錯体の触媒としての活性が高く好ましい。さらに、その中でも、トリシクロヘキシルホスフィンを用いて製造したルテニウムカルベン錯体が酸化され難く、特に好ましい。 Examples of the phosphine compound represented by the general formula (II) used in the present invention include triisopropylphosphine, tributylphosphine, tri (hexane-2-yl) phosphine, tricyclopentylphosphine, tricyclohexylphosphine, and tricyclooctylphosphine. Etc. Among them, the activity as a catalyst of a ruthenium carbene complex from which tricyclopentylphosphine or tricyclohexylphosphine is finally obtained is preferable. Furthermore, among them, a ruthenium carbene complex produced using tricyclohexylphosphine is particularly preferable because it is difficult to be oxidized.
本発明で用いるハロゲノ化合物は、上記一般式（III）で表されるものであり、上記一般式（III）中、Ｒ３は置換基を有してもよい芳香族炭化水素基を示し、Ｘ２はハロゲン原子を示す。
一般式（III）中のＲ３である置換基を有してもよい芳香族炭化水素基としては、フェニル基、トリル基、メシチル基などが挙げられ、その中でも入手の容易性からフェニル基が好ましい。
一般式（III）中のＸ２であるハロゲン原子としては、塩素、臭素、ヨウ素が挙げられ、その中でも入手の容易性から塩素が好ましい。
The halogeno compound used in the present invention is represented by the general formula (III). In the general formula (III), R 3 represents an aromatic hydrocarbon group which may have a substituent, and X 2 represents a halogen atom.
Examples of the aromatic hydrocarbon group which may have a substituent represented by R 3 in the general formula (III) include a phenyl group, a tolyl group, and a mesityl group. preferable.
Examples of the halogen atom that is X 2 in the general formula (III) include chlorine, bromine, and iodine. Among these, chlorine is preferable because of its availability.
本発明の上記一般式（III）で表されるハロゲノ化合物としては、例えば、塩化ベンザル、臭化ベンザル、α,α−ジクロロキシレン、α,α−ジブロモキシレンなどが挙げられる。その中でも、入手の容易性から塩化ベンザル及び臭化ベンザルが好ましい。 Examples of the halogeno compound represented by the general formula (III) of the present invention include benzal chloride, benzal bromide, α, α-dichloroxylene, α, α-dibromoxylene and the like. Among them, benzal chloride and benzal bromide are preferable because of their availability.
本発明における還元性金属としては、例えば、リチウム、ナトリウム、カリウム、マグネシウム、鉄、亜鉛、アルミニウムなどが挙げられる。その中でも、マグネシウム及び亜鉛が取り扱いが容易で反応性も高いことから好ましい。 Examples of the reducing metal in the present invention include lithium, sodium, potassium, magnesium, iron, zinc, aluminum and the like. Among these, magnesium and zinc are preferable because they are easy to handle and have high reactivity.
上記一般式（IV）で表されるルテニウムカルベン錯体を製造するに当たり、上記一般式（I）で表されるルテニウム錯体１モルに対して一般式（II）で表されるホスフィン化合物を２モル以上、一般式（III）で表されるハロゲノ化合物を２モル以上、及び還元性金属を２グラム当量以上の割合で用いる。
この中で、一般式（II）で表されるホスフィン化合物は２モル以上、１０モル以下の割合で用いることが好ましい。これ以上では、製造後に残存するホスフィン化合物の量が多くなり、これを除くために溶媒を多く使用せねばならないことから結果として目的のルテニウムカルベン錯体の収率が低下するので好ましくない。また、一般式（III）で表されるハロゲノ化合物は２モル以上、１０モル以下の割合で用いることが好ましい。これ以上では、ハロゲノ化合物同士が脱ハロゲンして２量体化したスチルベン構造を有する化合物を生成する副反応が起こり易く好ましくない。また、還元性金属は２グラム当量以上、５０グラム当量以下の割合で用いることが好ましい。これ以上では、反応終了後に発生する濾滓の量が増えるだけであり好ましくない。
In producing the ruthenium carbene complex represented by the general formula (IV), 2 moles or more of the phosphine compound represented by the general formula (II) with respect to 1 mole of the ruthenium complex represented by the general formula (I). The halogeno compound represented by the general formula (III) is used in a proportion of 2 mol or more, and the reducing metal is used in a proportion of 2 gram equivalent or more.
In this, it is preferable to use the phosphine compound represented by general formula (II) in the ratio of 2 mol or more and 10 mol or less. Above this, the amount of the phosphine compound remaining after production increases, and a large amount of solvent must be used to remove the phosphine compound, resulting in a decrease in the yield of the target ruthenium carbene complex. Moreover, it is preferable to use the halogeno compound represented by general formula (III) in the ratio of 2 mol or more and 10 mol or less. Above this, a side reaction that produces a compound having a stilbene structure in which halogeno compounds are dehalogenated to form a dimer is not preferable. Moreover, it is preferable to use a reducing metal in the ratio of 2 gram equivalent or more and 50 gram equivalent or less. Above this, the amount of filter cake generated after completion of the reaction only increases, which is not preferable.
上記一般式（IV）で表されるルテニウムカルベン錯体を製造するに当たり、その操作方法は次のとおりである。
不活性ガス雰囲気とした攪拌装置付きの反応器に、一般式（I）で表されるルテニウム錯体、一般式（II）で表されるホスフィン化合物、一般式（III）で表されるハロゲノ化合物、還元性金属及び反応溶媒を仕込む。反応溶媒としては、ベンゼン、トルエン、キシレンなどの芳香族系溶媒、ジエチルエーテル、テトラヒドロフランなどのエーテル系溶媒などが挙げられる。反応温度は０〜１００℃、好ましくは２０℃〜７０℃とする。反応時間として通常３０分〜５時間行うことで、目的の一般式（IV）で表されるルテニウムカルベン錯体が生成する。反応終了液からの一般式（IV）で表されるルテニウムカルベン錯体の回収と精製は、例えば、濾過、蒸発乾固、溶媒洗浄、減圧乾燥など通常の操作によって行うことができる。
In producing the ruthenium carbene complex represented by the general formula (IV), the operation method is as follows.
In a reactor equipped with an agitator with an inert gas atmosphere, a ruthenium complex represented by the general formula (I), a phosphine compound represented by the general formula (II), a halogeno compound represented by the general formula (III), A reducing metal and a reaction solvent are charged. Examples of the reaction solvent include aromatic solvents such as benzene, toluene and xylene, and ether solvents such as diethyl ether and tetrahydrofuran. The reaction temperature is 0 to 100 ° C, preferably 20 to 70 ° C. When the reaction time is usually 30 minutes to 5 hours, the desired ruthenium carbene complex represented by the general formula (IV) is produced. Recovery and purification of the ruthenium carbene complex represented by the general formula (IV) from the reaction end solution can be performed by usual operations such as filtration, evaporation to dryness, solvent washing, and drying under reduced pressure.
以下、実施例により本発明を具体的に説明する。
（ジクロロビス（トリシクロヘキシルホスフィン）ベンジリデンルテニウムの合成）
温度計、攪拌羽根を取付け、窒素ガス雰囲気にした１００ｍｌの四つ口フラスコに、一般式（I）で表されるルテニウム錯体としてジクロロトリス（トリフェニルホスフィン）ルテニウムを０．９５９（ｇ）（１．００ｍｍｏｌ）、一般式(II)で表されるホスフィン化合物としてトリシクロヘキシルホスフィンを１．１２（ｇ）（４．００ｍｍｏｌ）、一般式(III)で表されるハロゲノ化合物として塩化ベンザルを０．３２２（ｇ）（２．００ｍｍｏｌ）、還元性金属として粉末状亜鉛を１．３１（ｇ）（２０．０ｍｍｏｌ）及びトルエンを５２（ｇ）仕込んで、攪拌を開始し５５℃で２時間反応させ、濃赤褐色の反応液を得た。
反応液を濾過して濾滓を除去し、得られた濾液をロータリーエバポレーターで蒸発乾固した。これによって得られた黒色の粘稠物にメタノール２３（ｇ）を加えて攪拌したのち濾過し、濾紙上に茶褐色粉末を得た。この茶褐色粉末をアセトン５ｍｌで２回洗浄したところ赤紫色粉末となった。これを減圧乾燥して赤紫色粉末０．５１８（ｇ）（収率６３％）を得た。
このものを重クロロホルムに溶解させて１Ｈ−ＮＭＲ測定したスペクトルは、試薬として市販されているジクロロビス（トリシクロヘキシルホスフィン）ベンジリデンルテニウムのスペクトルと同一であった。
Hereinafter, the present invention will be described specifically by way of examples.
(Synthesis of dichlorobis (tricyclohexylphosphine) benzylidene ruthenium)
To a 100 ml four-necked flask equipped with a thermometer and a stirring blade and in a nitrogen gas atmosphere, 0.959 (g) (1) of dichlorotris (triphenylphosphine) ruthenium as the ruthenium complex represented by the general formula (I) .00 mmol), 1.12 (g) (4.00 mmol) of tricyclohexylphosphine as the phosphine compound represented by general formula (II), and 0.322 of benzal chloride as the halogeno compound represented by general formula (III). (G) (2.00 mmol), 1.31 (g) (20.0 mmol) of powdery zinc as a reducing metal and 52 (g) of toluene were charged, stirring was started, and the reaction was performed at 55 ° C. for 2 hours. A deep red-brown reaction solution was obtained.
The reaction solution was filtered to remove the filter cake, and the obtained filtrate was evaporated to dryness on a rotary evaporator. Methanol 23 (g) was added to the black viscous material thus obtained and stirred, followed by filtration to obtain a brown powder on the filter paper. When this brown powder was washed twice with 5 ml of acetone, a reddish purple powder was obtained. This was dried under reduced pressure to obtain 0.518 (g) of reddish purple powder (yield 63%).
The spectrum obtained by dissolving this in deuterated chloroform and measured by 1 H-NMR was identical to the spectrum of dichlorobis (tricyclohexylphosphine) benzylidene ruthenium commercially available as a reagent.
Claims (6)
The method for producing a ruthenium carbene complex according to any one of claims 1 to 5, wherein the reducing metal is magnesium or zinc.
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