CN109970814A - Pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline and preparation method thereof - Google Patents
Pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline and preparation method thereof Download PDFInfo
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- CN109970814A CN109970814A CN201910323217.9A CN201910323217A CN109970814A CN 109970814 A CN109970814 A CN 109970814A CN 201910323217 A CN201910323217 A CN 201910323217A CN 109970814 A CN109970814 A CN 109970814A
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- pyridine
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- nnn
- bipyridyl
- imidazoline
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- 150000003304 ruthenium compounds Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003446 ligand Substances 0.000 claims abstract description 16
- ZQTILGDVDYWICD-UHFFFAOYSA-N 6-pyridin-2-ylpyridine-2-carboxylic acid Chemical compound OC(=O)C1=CC=CC(C=2N=CC=CC=2)=N1 ZQTILGDVDYWICD-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000010992 reflux Methods 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 7
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 claims abstract description 7
- 125000003118 aryl group Chemical group 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 230000003647 oxidation Effects 0.000 claims abstract description 3
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 69
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 58
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 23
- -1 amide compound Chemical class 0.000 claims description 17
- 239000007787 solid Substances 0.000 claims description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- 210000000080 chela (arthropods) Anatomy 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 150000004982 aromatic amines Chemical class 0.000 claims description 7
- 150000001414 amino alcohols Chemical class 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000004809 thin layer chromatography Methods 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims 1
- 239000007858 starting material Substances 0.000 abstract description 2
- 125000001309 chloro group Chemical group Cl* 0.000 abstract 2
- 238000005576 amination reaction Methods 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 36
- 239000002585 base Substances 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000004009 13C{1H}-NMR spectroscopy Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 235000011121 sodium hydroxide Nutrition 0.000 description 8
- 238000001816 cooling Methods 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- 238000000607 proton-decoupled 31P nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- LFXADRFDJKXQRA-UHFFFAOYSA-L dichlororuthenium phosphane Chemical compound P.Cl[Ru]Cl LFXADRFDJKXQRA-UHFFFAOYSA-L 0.000 description 3
- 239000003480 eluent Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QLZHLNAALBJVOE-UHFFFAOYSA-N 6-pyridin-2-ylpyridine-2-carbonitrile Chemical compound N#CC1=CC=CC(C=2N=CC=CC=2)=N1 QLZHLNAALBJVOE-UHFFFAOYSA-N 0.000 description 2
- BRPZDFQCWRHMJF-UHFFFAOYSA-N CC1=CC=C(C=C1)N2CC(N=C2)C(C)(C)C Chemical class CC1=CC=C(C=C1)N2CC(N=C2)C(C)(C)C BRPZDFQCWRHMJF-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- XTHPWXDJESJLNJ-UHFFFAOYSA-N sulfurochloridic acid Chemical compound OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 2
- VPSSPAXIFBTOHY-LURJTMIESA-N (2s)-2-amino-4-methylpentan-1-ol Chemical group CC(C)C[C@H](N)CO VPSSPAXIFBTOHY-LURJTMIESA-N 0.000 description 1
- KIKATWFLYDKKOL-UHFFFAOYSA-N 1-oxido-2-pyridin-2-ylpyridin-1-ium Chemical class [O-][N+]1=CC=CC=C1C1=CC=CC=N1 KIKATWFLYDKKOL-UHFFFAOYSA-N 0.000 description 1
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 1
- ONIKNECPXCLUHT-UHFFFAOYSA-N 2-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1Cl ONIKNECPXCLUHT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- JBZRLVKMCLOFLG-UHFFFAOYSA-N O=S=Cl Chemical compound O=S=Cl JBZRLVKMCLOFLG-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 210000004209 hair Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- MTNDZQHUAFNZQY-UHFFFAOYSA-N imidazoline Chemical compound C1CN=CN1 MTNDZQHUAFNZQY-UHFFFAOYSA-N 0.000 description 1
- 125000002636 imidazolinyl group Chemical group 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses pincerlike ruthenium compounds of one kind asymmetric NNN ' containing pyridine-pyridine-imidazoline and preparation method thereof, and general formula is as follows:, wherein R1For C1‑C15Alkyl, aryl, R2For aryl.The synthetic method of such pincerlike ruthenium compound is: by 2,2- bipyridyl by hydrogen peroxide oxidation, itrile group hydrolyzes and obtains 2,2- bipyridyl -6- carboxylic acid, and for 2,2- bipyridyl -6- carboxylic acids using chloro, amination, then chloro, cyclization obtains ligand, ligand and RuCl2(PPh3)3The pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline is obtained in reflux in toluene.The present invention provides a kind of with 2,2- bipyridyl cheap and easy to get for starting material, synthesizes easy, the easy method of asymmetric pincerlike ruthenium compound.
Description
Technical field
The invention belongs to metal-organic synthesis and applied technical field, it is related to non-containing pyridine-pyridine-imidazoline
Pincerlike ruthenium compound of symmetrical NNN ' and preparation method thereof.
Background technique
Pincerlike metallic compound is composed of tridentate ligand and metal center, by adjusting the substitution on pincer ligand
Group, the space structure and cloud density of adjustable complex.In numerous coordinating groups, imidazoline, which has, to be easy to repair
The features such as decorations, stable structure, thus get the attention.By the difference of chiral amino alcohol in synthesis process, formation has
The imidazoline ring of different structure to adjust the three-dimensional effect of ligand, and then influences its activity in catalysis reaction.Previous
Research in, there are many synthesis about pincerlike compound, including symmetric form and asymmetrical type, symmetric form include NCN type,
PCP type, CCC type, asymmetrical type include PCN type, CCN type, PNN type etc..Pincerlike metallic compound is due to its unique three teeth knot
Structure makes it have unique property, such compound has been widely used in organic synthesis, luminescent material, supermolecule at present
The multiple fields such as chemistry, molecular recognition are especially rapidly developed in the application of catalytic field in recent years.
By in consideration of it, present invention design has synthesized a kind of novel asymmetric NNN ' type pincer ruthenium compound.
Summary of the invention
Technical problem to be solved by the invention is to provide pincerlike ruthenium compound of a kind of asymmetric NNN ' and preparation method thereof,
By adjusting R1, R2Substituent group on group, thus it is possible to vary the electronic effect and three-dimensional effect of complex, thus modulating compound
Activity in catalysis reaction.
In order to solve the above technical problems, the invention adopts the following technical scheme:
The pincerlike ruthenium compound of one kind asymmetric NNN ' containing pyridine-pyridine-imidazoline, general structure are as follows:
,
Wherein R1For C1-C15Alkyl, aryl, R2For aryl.
The preparation method is as follows: the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline synthesizes by the following method:
With cheap 2,2'- bipyridyl for starting material, 2,2'- bipyridyls react generation 2 with hydrogen peroxide in trifluoroacetic acid solution,
2 '-bipyridyl -1- oxides, then, 2,2 '-bipyridyl -1- oxides and trimethyl nitrile silane, chlorobenzoyl chloride are in anhydrous dichloro
It is reacted in methane and obtains within 4 days 2,2 '-bipyridyl -6- formonitrile HCNs, hydrolysis occurs in alkali and obtains 2,2- for 2,2 '-bipyridyl -6- formonitrile HCNs
2,2- bipyridyl -6- carboxylic acid is flowed back in thionyl chloride, steams thionyl chloride, anhydrous dichloromethane is added by bipyridyl -6- carboxylic acid
Alkane dissolution, it is anti-in room temperature after being added dropwise then in the anhydrous methylene chloride solution that condition of ice bath is added dropwise to chiral amino alcohol
It should stay overnight, then be spin-dried for reaction solution, continue to flow back in thionyl chloride, after reflux, steam thionyl chloride, be added anhydrous
Methylene chloride dissolution, is equally added dropwise in the anhydrous methylene chloride solution of aromatic amine, after being added dropwise, in room under condition of ice bath
Temperature reaction overnight, is then added 10% sodium hydrate aqueous solution, extracts, dry, concentration, and thin-layer chromatography is isolated asymmetric
NNN ' pincer ligand.By NNN ' pincer ligand and RuCl2(PPh3)3In reflux in toluene, atropurpureus solid is precipitated, it is as non-right
Claim the pincerlike ruthenium compound of NNN '.
Specific steps are as follows:
(1) 2,2- bipyridyl is passed through into hydrogen peroxide oxidation, itrile group, hydrolysis obtains 2,2- bipyridyl -6- carboxylic acid；
(2) 2,2- bipyridyl -6- carboxylic acid is flowed back in thionyl chloride, then boils off excessive thionyl chloride, ice bath instills hand
Property amino alcohol anhydrous methylene chloride solution in, after being added dropwise, reaction overnight, be then spin-dried for obtaining amide compound；
(3) thionyl chloride is added into amide compound and continues back flow reaction, then boil off excessive thionyl chloride, be added anhydrous
Methylene chloride and triethylamine, then aromatic amine is added dropwise in ice bath, is stirred overnight at room temperature, is eventually adding the aqueous solution of sodium hydroxide, after
It is continuous to be stirred overnight, it extracts, dry, concentration, thin-layer chromatography obtains asymmetric pincer ligand；
(4) asymmetric pincer ligand and RuCl2(PPh3)3It reacts in reflux in toluene, cools down after reaction, be directly precipitated solid
Body is washed with ether to get target compound is arrived.
Further, the molar ratio of 2,2- bipyridyl -6- carboxylic acid and thionyl chloride is 1:(7-21 in the step (2)), 2,
2- bipyridyl -6- carboxylic acid back flow reaction 8-12h in thionyl chloride, 2, the 2- bipyridyl -6- carboxylic acid and chiral amino alcohol
Molar ratio is 1:(1-2).
Further, the molar ratio of amide compound and aromatic amine is 1:(1-2 in the step (3)).
Further, amide compound return time in thionyl chloride is 8-12h in the step (3).
Further, the molar ratio of amide compound and thionyl chloride is 1:(7-21 in the step (3)), amide compound
Molar ratio with triethylamine, sodium hydroxide is 1:6:(8-12).
Further, room temperature is stirred to react 8-16h after the pure and mild aromatic amine of chiral amino is added dropwise in ice bath.
Further, the aqueous solution of sodium hydroxide is added in the step (3), continues to be stirred to react 8-12h, sodium hydroxide
The mass concentration of aqueous solution is 10%.
Further, in the step (4), asymmetric pincer ligand and RuCl2(PPh3)3The ratio between the amount of substance be 1:(1-
2), reflux time is 2-5 hours.
Beneficial effects of the present invention: the present invention relates to the pincerlike ruthenium chemical combination of one kind asymmetric NNN ' containing pyridine-pyridine-imidazoline
The synthesis of object, such compound and traditional rhodium, the metallic compounds such as palladium are compared, relatively inexpensively, meanwhile, with oxazoline
It closes object to compare, other substituent groups can be introduced on NR group, change the electronic effect and three-dimensional effect of complex with this, from
And activity of the modulating compound in catalysis reaction.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described.It should be understood that following embodiment is merely to illustrate this
The person skilled in the art of the range of invention and is not intended to limit the present invention, the field can make one according to the content of foregoing invention
A little nonessential modifications and adaptations.
Embodiment one
The preparation of 2,2'- bipyridyl -6- carboxylic acid: -6 formonitrile HCN of 2,2 '-bipyridyl (1.0 g, 5.5 mmol) and sodium hydroxide
(0.85 g, 21 mmol) one hour of back flow reaction in the mixed solution of alcohol-water (10 mL:10 mL), solution are cooling
Concentrated hydrochloric acid is added afterwards and is acidified to pH=3.8 or so, has white solid precipitation, then filters, wash solid with ice water, place into
Vacuum oven drying is to get to 2,2- bipyridyl -6- carboxylic acid.Yield: 0.92 g, 83%；Fusing point: 133-134oC.1H NMR
(400 MHz, d 6 -DMSO) δ 13.29 (s, 1H), 8.72 (d, J = 5.0 Hz, 1H), 8.59 (dd, J =
7.6, 1.3 Hz, 1H), 8.55 (d, J = 7.9 Hz, 1H), 8.17-8.08 (m, 2H), 8.00 (ddd, J =
7.6, 7.6, 1.8 Hz, 1H), 7.51 (ddd, J = 7.6, 4.8, 1.3 Hz, 1H); 13C{1H} NMR (100
MHz, d 6 -DMSO) δ 166.0, 155.2, 154.5, 149.3, 148.0, 138.7, 137.4, 124.8,
124.6, 123.5, 121.1. IR(KBr pellets, cm−1): 3436, 3372, 3058, 1698, 1615,
1583, 1534, 1471, 1754, 1259, 1169, 765, 713. HRMS (ESI-TOF) m/z: [M + H]+
calcd for C11H9N2O2 201.0659, found 201.0660.
Embodiment two
RuCl2(PPh3)3Preparation: by 1gRuCl3·3H2O is added in 150 mL methanol, and flow back 5min, is added after cooling
6.029 gPPh3, continue the 3h that flows back, stops reaction, it is cooling, by glossiness crystallization is precipitated in hot solution, filters, crystallization is used
Ether washing is dried afterwards for several times.Brown solid, yield 83.7%, fusing point: 145-146oC。1H NMR (400MHz, CDCl3) δ
7.71-7.63 (dd, J = 12.0, 7.5 Hz, 6H), 7.58-7.51 (dd, J = 7.5, 7.5 Hz, 3H),
7.50-7.42 (m, 6H). 13C{1H} NMR (100 MHz, CDCl3) δ 133.1, 132.2, 132.1, 131.9,
128.6,128.5.31P{1H} NMR (162 MHz,CDCl3) δ 29.0 (s, PPh3), IR (cm-1): 3049,
1480, 1432, 1086, 741, 691, 514, 495。
Embodiment three
The pincerlike ruthenium compound containing the asymmetric NNN ' of pyridine-pyridine-imidazoline of the present embodiment the preparation method is as follows:
(1) (S) -6- (4- (tert-butyl) -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl system
Standby: 2,2- bipyridyl -6- carboxylic acids (10mmol) back flow reaction 8h in thionyl chloride solution (5 mL), revolving remove excessive Asia
Chlorosulfuric acid give light yellow oil is dissolved in anhydrous methylene chloride solution, under condition of ice bath, is added dropwise into dissolved with L-
(11mmol, 1.29 g) and in the anhydrous methylene chloride solution of triethylamine (30mmol, 4.2 mL), are added dropwise tertiary leucinol
Afterwards, reaction is stayed overnight at room temperature.After reaction, reactant is spin-dried for, ethyl acetate is added, is filtered to remove insoluble matter, filtrate
It is continuously added after being spin-dried for and reacts 8h under thionyl chloride (5 mL) reflux state, revolving removes excessive thionyl chloride and obtains rufous oil
Shape object is dissolved in anhydrous methylene chloride solution, under condition of ice bath, be added dropwise into dissolved with para-totuidine (11mmol,
1.2 g) and in the anhydrous methylene chloride solution of triethylamine (60 mmol, 8 mL), after being stirred overnight at room temperature, add 10% hydrogen
Aqueous solution of sodium oxide (35 mL), room temperature continue to stir 8-12h, after, liquid separation, water phase is extracted with dichloromethane 3 times, merges
Organic phase is added anhydrous magnesium sulfate drying, filters, be spin-dried for, column chromatography for separation (eluant, eluent ratio PE/EA=3/1 ~ 1/10)
To corresponding NNN ' ligand.Brown solid;Yield: 52%；Fusing point: 119-121oC。1H NMR (400 MHz, CDCl3) δ
8.57 (d, J = 4.7 Hz, 1H), 8.33 (d, J = 7.7 Hz, 1H), 7.99 (d, J = 7.7, Hz,
1H), 7.84 (t, J = 7.7 Hz, 1H), 7.53 (ddd, J = 7.7, 7.7, 1.8 Hz, 1H), 7.37 (d,J = 8.0 Hz, 1H), 7.19 (ddd, J = 7.5, 4.8, 1.2 Hz, 1H), 6.99 (d, J = 8.0 Hz,
2H), 6.80 (d, J = 8.0 Hz, 2H), 4.23-4.13 (m, 1H), 4.10-4.01 (m, 1H), 3.71 (t,J = 8.4 Hz, 1H), 2.26 (s, 3H), 1.03 (s, 9H). 13C{1H} NMR (100 MHz, CDCl3) δ
160.3, 155.7, 154.8, 149.4, 148.8, 141.6, 137.5, 136.5, 133.3, 129.1, 124.1,
123.7, 123.5, 121.4, 121.3, 74.2, 55.6, 34.3, 26.0, 20.8. IR(cm-1): 2949,
2860, 1592, 1560, 1515, 1463, 1432, 1388, 1362, 1161, 1144, 992, 821, 786,
750, 564. HRMS (ESI-TOF) m/z: [M + H]+calcd for C24H27N4 371.2230, found
371.2238.
(2) (S) -6- (4- (tert-butyl) -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl triphen
The preparation of base phosphine dichloride ruthenium: be added in the Shrek bottle equipped with 100 mL for being stirred at reflux device (S) -6- (4- (tertiary fourth
Base) -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl (0.4mmol, 148mg), three (triphenyls
Phosphine) ruthenous chloride (0.4mmol, 383mg) and 30 mL toluene, back flow reaction 3h, after reaction, cooling under a nitrogen atmosphere
Solid is precipitated, filters, is washed with ether to get product (170 mg) is arrived.Yield 53%.Violet solid, fusing point: > 300oC。1H
NMR (600 MHz, CDCl3) δ 9.55-9.45 (m, 1H), 7.74 (d, J = 7.9 Hz, 1H), 7.63 (d,J = 7.9, Hz, 1H), 7.48-7.37 (m, 7H), 7.25-7.03 (m, 13H), 6.93-6.69 (m, 2H),
6.48 (d, J = 7.9 Hz, 1H), 4.07-3.98 (m, 1H), 3.97-3.90 (m, 1H), 3.88-3.77 (m,
1H), 2.38 (s, 3H), 1.27 (s, 9H). 13C{1H} NMR (150 MHz, CDCl3) δ160.3, 157.9,
138.3, 136.8, 134.8, 133.13, 133.11, 131.6, 131.3, 130.1, 128.9, 128.2,
127.7, 127.6, 126.4, 125.0, 121.1, 120.5, 57.1, 35.9, 29.8, 27.4, 21.1. 31P
{1H} NMR (162 MHz, CDCl3) δ 42.2 (s, PPh3). IR (cm−1): ν3053, 2950, 2869, 1739,
1548, 1524, 1511, 1490, 1480, 1426, 1374, 1363, 1296, 1084, 833, 779, 749,
699, 685, 524, 510, 500.HRMS (ESI-TOF) m/z: [M – 2Cl-]2+calcd for C42H41N4PRu
367.1051, found 367.1057.
Example IV
The pincerlike ruthenium compound containing the asymmetric NNN ' of pyridine-pyridine-imidazoline of the present embodiment the preparation method is as follows:
(1) (S) -6- (4- isopropyl -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl preparation:
2,2- bipyridyl -6- carboxylic acids (10mmol) back flow reaction 8h in thionyl chloride solution (5 mL), revolving remove excessive sulfurous
Acyl chlorides give light yellow oil is dissolved in anhydrous methylene chloride solution, under condition of ice bath, is added dropwise into dissolved with L- figured silk fabrics
Ammonia alcohol (11mmol, 1.13 g) and in the anhydrous methylene chloride solution of triethylamine (30mmol, 4.2 mL), after being added dropwise,
Reaction is stayed overnight at room temperature.After reaction, reactant is spin-dried for, ethyl acetate is added, insoluble matter is filtered to remove, after filtrate is spin-dried for
It continuously adding and reacts 8h under thionyl chloride (5 mL) reflux state, revolving removes excessive thionyl chloride and obtains rufous grease,
It is dissolved in anhydrous methylene chloride solution, under condition of ice bath, is added dropwise into (11mmol, 1.2 g) dissolved with para-totuidine
In the anhydrous methylene chloride solution of triethylamine (60mmol, 8 mL), after being stirred overnight at room temperature, 10% sodium hydroxide is added
Aqueous solution (35 mL), room temperature continue to stir 8-12h, after, liquid separation, water phase is extracted with dichloromethane 3 times, merge organic phase,
It is dry that anhydrous magnesium sulfate is added, filters, is spin-dried for, column chromatography for separation (eluant, eluent ratio PE/EA=3/1 ~ 1/10) obtains accordingly
NNN ' ligand.Brown solid；Yield: 50%；Fusing point: 82-84oC。1H NMR (400 MHz, CDCl3) δ 8.58 (d, J =
5.1 Hz, 1H), 8.33 (d, J = 7.5 Hz, 1H), 7.94 (d, J = 7.5, Hz, 1H), 7.84 (t, J
= 8.0 Hz, 1H), 7.54 (ddd, J = 7.7, 7.7, 1.8 Hz, 1H), 7.40 (d, J = 8.0 Hz,
1H), 7.21 (ddd, J = 7.5, 4.9, 1.2 Hz, 1H), 6.99 (d, J = 8.0 Hz, 2H), 6.80 (d,J = 8.0 Hz, 2H), 4.20-4.07 (m, 2H), 3.75-3.65 (m, 1H), 2.26 (s, 3H), 2.01-
1.92 (m, 1H), 1.10 (d, J = 6.9 Hz, 3H), 1.00 (d, J = 6.9 Hz, 3H). 13C{1H} NMR
(100 MHz, CDCl3 ) δ 160.3, 155.6, 154.9, 149.4, 148.8, 141.4, 137.4, 136.5,
133.3, 129.1, 124.1, 123.7, 123.3, 121.5, 121.4, 70.6, 56.9, 33.2, 20.9,
19.1, 18.1. IR(cm-1): 2956, 2870, 1590, 1561, 1514, 1462, 1432, 1390, 1267,
1161, 1145, 1046, 992, 819, 786, 751, 715, 635, 566. HRMS (ESI-TOF) m/z: [M +
H]+calcd for C23H25N4 357.2074, found 357.2078.
(2) (S) -6- (4- (isopropyl) -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl triphen
The preparation of base phosphine dichloride ruthenium: be added in the Shrek bottle equipped with 100 mL for being stirred at reflux device (S) -6- (4- (isopropyl
Base) -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl (0.4mmol, 142mg), three (triphenyls
Phosphine) ruthenous chloride (0.4mmol, 383mg) and 30 mL toluene, 3 h of back flow reaction, after reaction, cooling under a nitrogen atmosphere
Solid is precipitated, filters, is washed with ether to get product (220 mg) is arrived.Violet solid, yield: 70%；Fusing point: > 300oC。1H
NMR (600 MHz, CDCl3) δ 9.40-9.34 (m, 1H), 7.71 (d, J = 8.0 Hz, 1H), 7.52 (d,J = 8.0 Hz, 1H), 7.48-7.39 (m, 7H), 7.37-7.29 (m, 1H), 7.21-7.12 (m, 5H),
7.12-7.06 (m, 6H), 7.01 (t, J = 8.0 Hz, 1H), 6.94-6.86 (m, 2H), 6.33 (d, J =
8.0 Hz, 1H), 4.35-4.20 (m, 1H), 4.09-3.93 (m, 2H), 3.50-3.33 (m, 1H), 2.37(s,
3H), 1.14 (d, J = 6.3 Hz, 3H), 0.95 (d, J = 6.3 Hz, 3H). 13C{1H} NMR (150 MHz,
CDCl3) δ 160.7, 158.1, 153.6, 139.4, 137.2, 134.6, 132.9, 132.8, 132.3,
132.1, 130.2, 128.9, 128.2, 127.8, 127.7, 126.7, 126.1, 124.2, 121.0, 120.1,
55.5, 29.2, 21.1, 20.3, 15.9. 31P{1H} NMR (162 MHz, CDCl3) δ 42.5 (s, PPh3). IR
(cm−1): ν3049, 2963, 2838, 2860, 1552, 1527, 1509, 1485, 1433, 1423, 1373,
1284, 1155, 1087, 1037, 838, 779, 747, 698, 523, 510, 500.HRMS (ESI-TOF) m/z:
[M – 2Cl-]2+calcd for C41H39N4PRu 360.0973, found 360.0980.
Embodiment five
The pincerlike ruthenium compound containing the asymmetric NNN ' of pyridine-pyridine-imidazoline of the present embodiment the preparation method is as follows:
(1) (S) -6- (4- benzyl -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl preparation: 2,
2- bipyridyl -6- carboxylic acid (10mmol) back flow reaction 8h in thionyl chloride solution (5 mL), revolving remove excessive thionyl
Chlorine give light yellow oil is dissolved in anhydrous methylene chloride solution, under condition of ice bath, is added dropwise into dissolved with L- phenylpropyl alcohol
Ammonia alcohol (11mmol, 1.82 g) and in the anhydrous methylene chloride solution of triethylamine (30mmol, 4.2 mL), after being added dropwise,
Reaction is stayed overnight at room temperature.After reaction, reactant is spin-dried for, ethyl acetate is added, insoluble matter is filtered to remove, after filtrate is spin-dried for
It continuously adding and reacts 8h under thionyl chloride (5 mL) reflux state, revolving removes excessive thionyl chloride and obtains rufous grease,
It is dissolved in anhydrous methylene chloride solution, under condition of ice bath, is added dropwise into (11mmol, 1.2 g) dissolved with para-totuidine
In the anhydrous methylene chloride solution of triethylamine (60mmol, 8 mL), after room temperature overtime work overnight, 10% sodium hydroxide is added
Aqueous solution (35 mL), room temperature continue to stir 8-12h, after, liquid separation, water phase is extracted with dichloromethane 3 times, merge organic phase,
It is dry that anhydrous magnesium sulfate is added, filters, is spin-dried for, column chromatography for separation (eluant, eluent ratio PE/EA=3/1 ~ 1/10) obtains accordingly
NNN ' ligand.Brown solid；Yield 56%；Fusing point: 109-111oC。1H NMR (400 MHz, CDCl3) δ 8.58 (d, J=
4.7 Hz, 1H), 8.35 (d, J = 8.0 Hz, 1H), 7.93 (d, J = 7.7, Hz, 1H), 7.84 (t, J
= 7.7 Hz, 1H), 7.53 (ddd, J = 7.7, 7.7, 1.8 Hz, 1H), 7.38 (d, J = 8.0 Hz,
1H), 7.32-7.26 (m, 4H), 7.23-7.16 (m, 2H), 6.96 (d, J = 8.0 Hz, 2H), 6.67 (d,J = 8.0 Hz, 2H), 4.67-4.57 (m, 1H), 4.07 (t, J = 9.5 Hz, 1H), 3.76 (dd, J =
9.6, 7.4 Hz, 1H), 3.30 (dd, J = 13.6, 4.6 Hz, 1H), 2.90 (dd, J = 13.8, 9.0
Hz, 1H), 2.24 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3) δ 160.6, 155.5, 154.9,
148.9, 148.8, 141.0, 138.3, 137.5, 136.6, 133.6, 129.5, 129.1, 128.4, 126.4,
124.2, 123.7, 123.5, 121.6, 121.5, 65.5, 58.7, 42.2, 20.8. IR(cm-1): 3063,
3058, 2920, 2861, 1591, 1562, 1514, 1473, 1432, 1388, 1324, 1281, 1261, 1158,
1095, 1071, 992, 820, 786, 750, 728, 696, 635, 620, 599, 554, 513, 498, 465.
HRMS (ESI-TOF) m/z: [M + H]+calcd for C27H25N4 405.2074, found 405.2078.
(2) (S) -6- (4- (benzyl) -1- (p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl triphenyl
The preparation of phosphine dichloride ruthenium: be added in the Shrek bottle equipped with 100 mL for being stirred at reflux device (S) -6- (4- (benzyl) -1-
(p-methylphenyl) -4,5- dihydro -1HImidazoles -2- base) -2,2'- bipyridyl (0.4mmol, 162mg), three (triphenylphosphine) dichloros
Change ruthenium (0.4mmol, 383mg) and 30 mL toluene, under a nitrogen atmosphere 3 h of back flow reaction, it is after reaction, cooling to be precipitated admittedly
Body filters, and is washed with ether to get product (220 mg) is arrived.Violet solid, yield: 66%；Fusing point: > 300oC。1H NMR
(400 MHz, CDCl3) δ 9.33 (d, J = 5.3Hz, 1H), 7.77 (d, J = 7.8 Hz, 1H), 7.57-
7.49 (m, 2H), 7.48-7.42 (m, 6H), 7.39 (d, J = 7.4 Hz, 2H), 7.31 (t, J = 7.4
Hz, 2H), 7.23-7.16 (m, 5H), 7.14-7.08 (m, 8H), 6.98 (d, J = 7.7 Hz, 1H),
6.90-6.81 (m, 2H), 6.35 (d, J = 7.7 Hz, 1H), 4.84-4.75 (m, 1H), 4.57-4.45 (m,
1H), 3.85-3.73 (m, 2H), 3.12-3.01 (m, 1H), 2.35 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3) δ 163.3, 161.1, 158.2, 153.9, 153.4, 139.3, 139.2, 137.3, 134.6,
133.1, 133.0, 132.7, 132.3, 130.2, 129.4, 129.0, 128.5, 127.8, 127.7, 126.3,
126.1, 125,8, 124.2, 121.5, 120.4, 67.1, 61.3, 41.6, 21.1. 31P{1H} NMR (162
MHz, CDCl3) δ 43.2 (s, PPh3). IR (cm−1): ν3054, 2861, 1603, 1551, 1525, 1511,
1482, 1430, 1374, 1293, 1157, 1091, 1039, 827, 777, 754, 744, 697, 527, 514,
496. HRMS (ESI-TOF) m/z: [M – 2Cl]2+calcd for C45H39N4PRu 384.0973, found
384.0987.
Basic principles and main features and advantages of the present invention of the invention have been shown and described above.The technology people of the industry
Member is it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this hairs
Bright principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variations
It all fall within the protetion scope of the claimed invention with improvement.The claimed scope of the invention is by appended claims and its waits
Effect object defines.
Claims (9)
1. the pincerlike ruthenium compound of one kind asymmetric NNN ' containing pyridine-pyridine-imidazoline, it is characterised in that: the pincer ruthenium chemical combination
The structural formula of object is as follows:,
Wherein R1For C1-C15Alkyl or aryl, R2For aryl.
2. the preparation method of the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline according to claim 1,
Characterized by the following steps:
(1) 2,2- bipyridyl is passed through into hydrogen peroxide oxidation, itrile group, hydrolysis obtains 2,2- bipyridyl -6- carboxylic acid；
(2) 2,2- bipyridyl -6- carboxylic acid is flowed back in thionyl chloride, then boils off excessive thionyl chloride, ice bath instills hand
Property amino alcohol anhydrous methylene chloride solution in, after being added dropwise, reaction overnight, be then spin-dried for obtaining amide compound；
(3) thionyl chloride is added into amide compound and continues back flow reaction, then boil off excessive thionyl chloride, be added anhydrous
Methylene chloride and triethylamine, then aromatic amine is added dropwise in ice bath, is stirred overnight at room temperature, is eventually adding the aqueous solution of sodium hydroxide, after
It is continuous to be stirred overnight, it extracts, dry, concentration, thin-layer chromatography obtains asymmetric pincer ligand；
(4) asymmetric pincer ligand and RuCl2(PPh3)3It reacts in reflux in toluene, cools down after reaction, be directly precipitated solid
Body is washed with ether to get target compound is arrived.
3. the preparation method of the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline according to claim 2,
It is characterized by: the molar ratio of 2,2- bipyridyl -6- carboxylic acid and thionyl chloride is 1:(7-21 in the step (2)), 2,2- connection
Pyridine -6- carboxylic acid back flow reaction 8-12h in thionyl chloride, mole of 2, the 2- bipyridyl -6- carboxylic acid and chiral amino alcohol
Than for 1:(1-2).
4. the method for the pincerlike ruthenium compound of synthesis according to claim 2 asymmetric NNN ' containing pyridine-pyridine-imidazoline,
It is characterized by: the molar ratio of amide compound and aromatic amine is 1:(1-2 in the step (3)).
5. the preparation method of the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline according to claim 2,
It is characterized by: amide compound return time in thionyl chloride is 8-12h in the step (3).
6. the preparation method of the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline according to claim 2,
It is characterized by: the molar ratio of amide compound and thionyl chloride is 1:(7-21 in the step (3)), amide compound and three
Ethamine, sodium hydroxide molar ratio be 1:6:(8-12).
7. the preparation method of the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline according to claim 2,
It is characterized by: room temperature is stirred to react 8-16h after the pure and mild aromatic amine of chiral amino is added dropwise in ice bath.
8. the preparation method of the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline according to claim 2,
It is characterized by: the aqueous solution of sodium hydroxide is added in the step (3), continue to be stirred to react 8-12h, sodium hydroxide it is water-soluble
The mass concentration of liquid is 10%.
9. the preparation method of the pincerlike ruthenium compound of the asymmetric NNN ' containing pyridine-pyridine-imidazoline according to claim 2,
It is characterized by: in the step (4), asymmetric pincer ligand and RuCl2(PPh3)3The ratio between the amount of substance be 1:(1-2),
Reflux time is 2-5 hours.
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| CN110818689A (en) * | 2019-10-31 | 2020-02-21 | 华侨大学 | Pincer-shaped polypyridine-polypyrrole silver cluster compound containing five coordination sites as well as preparation method and application thereof |
| CN114591509A (en) * | 2022-03-16 | 2022-06-07 | 华中科技大学同济医学院附属协和医院 | Metal organic framework material with antioxidant activity |
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| CN110818689A (en) * | 2019-10-31 | 2020-02-21 | 华侨大学 | Pincer-shaped polypyridine-polypyrrole silver cluster compound containing five coordination sites as well as preparation method and application thereof |
| CN110818689B (en) * | 2019-10-31 | 2022-03-25 | 华侨大学 | Pincer-shaped polypyridine-polypyrrole silver cluster compound containing five coordination sites as well as preparation method and application thereof |
| CN114591509A (en) * | 2022-03-16 | 2022-06-07 | 华中科技大学同济医学院附属协和医院 | Metal organic framework material with antioxidant activity |
| CN114591509B (en) * | 2022-03-16 | 2023-02-17 | 华中科技大学同济医学院附属协和医院 | Metal organic framework material with antioxidant activity |
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