CN107163085A - A kind of preparation of chiral platinum complex crystal and purposes - Google Patents
A kind of preparation of chiral platinum complex crystal and purposes Download PDFInfo
- Publication number
- CN107163085A CN107163085A CN201710430760.XA CN201710430760A CN107163085A CN 107163085 A CN107163085 A CN 107163085A CN 201710430760 A CN201710430760 A CN 201710430760A CN 107163085 A CN107163085 A CN 107163085A
- Authority
- CN
- China
- Prior art keywords
- platinum complex
- complex crystal
- reaction
- chiral
- crystal
- 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.)
- Pending
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000013078 crystal Substances 0.000 title claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 8
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000010189 synthetic method Methods 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- XXRCUYVCPSWGCC-UHFFFAOYSA-N Ethyl pyruvate Chemical compound CCOC(=O)C(C)=O XXRCUYVCPSWGCC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229940117360 ethyl pyruvate Drugs 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims abstract description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011701 zinc Substances 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052725 zinc Inorganic materials 0.000 abstract description 3
- 125000005968 oxazolinyl group Chemical group 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- -1 oxazoline platinum Chemical compound 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000007333 cyanation reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 235000013832 Valeriana officinalis Nutrition 0.000 description 1
- 244000126014 Valeriana officinalis Species 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 229940054066 benzamide antipsychotics Drugs 0.000 description 1
- 150000003936 benzamides Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 150000008422 chlorobenzenes Chemical class 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical compound [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GZAJJDUWYRDMPO-UHFFFAOYSA-N methylsulfinylmethane;platinum Chemical compound [Pt].CS(C)=O GZAJJDUWYRDMPO-UHFFFAOYSA-N 0.000 description 1
- 238000000302 molecular modelling Methods 0.000 description 1
- ZHDORMMHAKXTPT-UHFFFAOYSA-N n-benzoylbenzamide Chemical compound C=1C=CC=CC=1C(=O)NC(=O)C1=CC=CC=C1 ZHDORMMHAKXTPT-UHFFFAOYSA-N 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000004424 polypyridyl Polymers 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229940127224 quinoline drug Drugs 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 0.000 description 1
- 235000016788 valerian Nutrition 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
- C07F15/0086—Platinum compounds
- C07F15/0093—Platinum compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
-
- 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
A kind of chiral platinum complex crystal, its chemical formula is as follows：（Ⅰ）The synthetic method of the chiral platinum complex crystal (I) be weigh it is double（The oxazolinyl of 4 4,5 dihydro of (R) isopropyl 2）Acetonitrile zinc 0.2662g does solvent dissolving with 30mL dichloromethane, adds Pt（DMSO）2Cl20.3406g, stops reaction after reacting 60 hours at room temperature, filtering adds dichloromethane, petroleum ether and absolute ethyl alcohol, volatilize to obtain a kind of new platinum complex monocrystalline naturally;The purposes of the chiral platinum complex crystal (I), is that the complex crystal shows good catalytic performance in the reaction of the Henle reaction and benzaldehyde and benzamide of ethyl pyruvate, and its conversion ratio is up to 41%, 56% and 40% respectively.
Description
First, technical field
The present invention relates to a kind of organometallic complex（Complex）And preparation method thereof, more particularly to platinum metal is organic
Complex and preparation method thereof, is exactly Yi Zhong oxazoline platinum complex crystal and its synthetic method.
2nd, background technology
Metal platinum complex has caused people's because of its potential using value in terms of anticancer and molecular magnet, fluorescent material
Extensive concern.The synthetic method of metal platinum complex has many document reports in recent years.【1-7】
1. A Comparative Antimicrobial Study In Between a Quinoline Drug and Its
Complexes: Spectral, Kinetic, and Molecular Modeling Investigations, Al-
Hazmi, Gamil A. A.; Saad, Fawaz A. Synthesis and Reactivity in Inorganic,
Metal-Organic, and Nano-Metal Chemistry (2015), 45(11), 1743-1757.
2. One-pot synthesis of dual-emitting BSA-Pt-Au bimetallic
nanoclusters for fluorescence ratiometric detection of mercury ions and
cysteine, Ding, Shou-Nian; Guo, Yun-Xia
From Analytical Methods (2015), 7(14), 5787-5793.
3. Five coordinate platinum(II) in [Pt(bpy)(cod)(Me)][SbF6]: a
structural and spectroscopic study, Klein, Axel; Neugebauer, Michael; Krest,
Alexander; Luening, Anna; Garbe, Simon; Arefyeva, Natalia; Schloerer, Nils ,
Inorganics (2015), 3(2), 118-138.
4. Synthesis and Reactivity of Platinum(II) cis-Dialkyl, cis-Alkyl
Chloro, and cis-Alkyl Hydrido Bis-N-heterocyclic Carbene Chelate Complexes
, Brendel, Matthias; Engelke, Rene; Desai, Vidya G.; Rominger, Frank;
Hofmann, Peter , Organometallics (2015), 34(12), 2870-2878.
5. The Challenge of Deciphering Linkage Isomers in Mixtures of Oligomeric
Complexes Derived from 9-Methyladenine and trans-(NH3)2PtII Units, Ibanez,
Susana; Mihaly, Bela; Sanz Miguel, Pablo J.; Steinborn, Dirk; Pretzer, Irene;
Hiller, Wolf; Lippert, Bernhard
Chemistry - A European Journal (2015), 21(15), 5794-5806.
6. Polypyridyl ruthenium complexes containing anchoring nitrile groups as
TiO2 sensitizers for application in solar cells , Mecchia Ortiz, Juan H.;
Longo, Claudia; Katz, Nestor E. Inorganic Chemistry Communications (2015),
55, 69-72.
7. Charge-bistable Pd(III)/Pd(II,IV) coordination polymers: phase
transitions and their applications to optical properties, Kumagai, Shohei;
Takaishi, Shinya; Iguchi, Hiroaki; Yamashita, Masahiro , Dalton Transactions
(2015), 44(18), 8590-8599。
3rd, the content of the invention
The present invention is intended to provide a kind of Pt-N metal organic complexes are so that applied to catalytic field, technical problem to be solved is selected for a post
It is elected to be as part and synthesizes Zn complex.
Platinum complex alleged by the present invention is a kind of be as with preparation as the complex shown in below formula：
（Ⅰ）.
Chemical name：Monochlor(in)ate（4 (R)-isopropyl -4,5- dihydro -2- oxazolinyls）- acetonitrile zinc platinum complex, letter
Claim complex (I).
The complex shown in the Henle reaction of ethyl pyruvate, silicon cyanation and reaction with benzamide compared with
Good catalytic performance, its conversion ratio is up to 41% and 40% respectively.
This synthetic method includes synthesis and separated, described synthesis be weigh it is double-（4 (R)-isopropyl -4,5- dihydros -
2- oxazolinyls）- acetonitrile zinc 0.2662g does solvent dissolving with 30mL dichloromethane, adds Pt（DMSO）2Cl2 0.3406g,
Stop reaction after reacting 60 hours at room temperature, filtering adds dichloromethane, petroleum ether and absolute ethyl alcohol, volatilizees naturally a kind of
New platinum complex monocrystalline.
Synthetic reaction is as follows：
The step of this synthetic method one obtains target product, and technique is simple, easy to operate.
The reaction mechanism of the reaction can be speculated as because the coordination ability of platinum and nitrogen-atoms is more than the coordination of zinc and nitrogen-atoms
Ability, therefore obtained a kind of new platinum complex.
4th, illustrate
Fig. 1 complex monochlor(in)ates（4 (R)-isopropyl -4,5- dihydro -2- oxazolinyls）The X- of-acetonitrile platinum complex crystal spreads out
Penetrate analysis chart.
5th, embodiment
1. platinous chloride dimethyl sulfoxide complex
In 100mL two-mouth bottles, platinous chloride 1.2042g, 10mLDMSO, dichloromethane 30mL are added, mixture is flowed back
60h, stops reaction, static, obtains dimethyl sulfoxide platinum complex solid, yield 45%；Elementary analysis：Test value：C: 11.78
%, H: 2.91%;Calculated value：C: 11.38%, H 2.86%; IR (KBr):1157,1134,450,430.
2. pair-（4- (R)-isopropyl -4,5- dihydro -2- oxazolinyls）The preparation of-acetonitrile Zn complex
In 100mL two-mouth bottles, under the conditions of anhydrous and oxygen-free, anhydrous ZnCl is added2 0.45g (3.30mmol), 40mL chlorobenzenes,
Four nitrile ethene 1.0g (7.81mmol), D- valerian ammonia alcohol 4g, mixture is flowed back 24h at high temperature, stops reaction, decompression with
Solvent is removed, residue water is dissolved, and use CHCl3(20mLx2) is extracted, organic phase anhydrous sodium sulfate drying, rotation
Solvent is removed, by crude product petroleum ether/dichloromethane (4:1) column chromatography, obtains white crystal, yield 52%；[a]5 D=-305.9
º (c=0.26, CH2Cl2)：1HNMR (500MHz, CDCl3, 27℃), δ (ppm) = 4.35(t, 4H), 4.16
(t, J=1Hz, 4H), 3.81~3.83 (m, 4H), 1.62~1.66 (m, 4H), 0.74~0.87 (dd, J=7Hz,
6.5Hz, 24 H); 13C NMR (75 MHz, CDCl3) 170.6(x2), 118.6(x2), 73.0(x4), 68.9
(x4), 68.5(x4), 31.8(x4), 19.2(x4), 15.7(x4)。IR :3443(s), 2963(s), 2200(s),
1609(s), 1533(s), 1484(s), 1432(s), 1391(m), 1371(w), 1341(w), 1312(w), 1251
(m), 1222(m), 1117(m), 1075(s), 953(m), 744(m), 566(w), 528(w), 457(w);Element
Analysis theories value：C:57.00%, H, 6.83%, N, 14.24%；Measured value：C:56.80%, H, 6.79%, N,
14.35%。
The preparation of monochlor(in)ate 3. (4 (R)-isopropyl -4,5- dihydro -2- oxazolinyls)-acetonitrile platinum complex crystal
Double-(4 (R)-isopropyl -4,5- dihydro -2- oxazolinyls)-acetonitrile zinc 0.2662g is weighed to make of 30mL dichloromethane
Solvent dissolves, and adds Pt (DMSO)2Cl20.3406g, stops reaction after reacting 60 hours at room temperature, filtering adds dichloro
Methane, petroleum ether and absolute ethyl alcohol, volatilize to obtain a kind of new platinum complex monocrystalline naturally；Yield 85%, fusing point：320-322
℃；[a]5 D=-923.1 ° of (c=0.156, CH3OH)；Elementary analysis C16H26N3O3PtSCl：Test value：C:33.60%, H:
4.73%, N:7.05%, S:5.58%；Calculated value：C:33.66%, H 4.59%, N:7.36%；S:5.61%；IR
(KBr):3443,2961,2924,2210,1627,1531, 1485,1450,1390,1245,1135,1081,1023,960,
805,731,567,445；
Match crystal volume data is as follows：
The typical bond distance's data of crystal：
The typical bond angle data of crystal：
Henle reaction application
0.0235g (7.5%mmol) complex (I), is placed in 25mL flasks, sequentially adds 1mL tetrahydrofurans, 0.25mL nitre
Methylmethane and 0.015mL ethyl pyruvates, stirring at normal temperature reaction 48h, separately sampled progress1HNMR detects that its conversion ratio is
41%；1H NMR(CDCl 3):δ) 4.86 (d, J=13.8Hz, 1H), 4.58 (d, J=13.8Hz, 1H), 4.34 (m, 2H),
3.85(s,1H),1.46(s,3H),1.33(t,J)7.2Hz, 3H).13C NMR(CDCl 3):δ=173.4,80.9,72.4,
63.0,23.8,13.9。
N, N '-（Phenylmethylene）The preparation of dibenzamide
In 25mL two-mouth bottles, add 0.0659g complexs I, 2mLTHF and chlorobenzene 2mL, 0.05mL benzaldehyde and
0.1302g benzamides, back flow reaction has crystal appearance after 48 hours：Detected with nuclear-magnetism, conversion ratio 40%;1HNMR
(500MHz, CDCl3, 27 DEG C), δ (ppm)=9.02 (d, J=7.77Hz, 2H), 7.91 (d, J=7.42Hz, 4H),
7.54 (t, J=7.4Hz, 2H), 7.47 (t, J=7.7Hz, 6H), 7.37 (t, J=7.7Hz, 2H), 7.30 (t, J=
7.3Hz, 1H), 7.03(t, J=7.9Hz, 1H)。
Silicon cyanation application
2- phenyl -2-（Three silyloxies）Propionitrile
The ml (3.3mmol) of 0.1mmol complex I, benzaldehyde 0.1mL, TMSCN 0.3,2mL absolute methanols, in succession
Added under 30 ~ 35 C, after 48 hours, add water quenching and go out after post layer（Petroleum ether/dichloromethane：5/1）, obtain colorless oil
Liquid, conversion ratio：56 %;1H NMR (300MHz, CDCl3) 7.56–7.59 (m, 0.9 Hz, 2H), 7.31–
7.34 (m, 3H), 5.43 (s, 1H), 0.16 (s, 9H). 13C NMR (75 MHz, CDCl3) 136.1, 128.8
(x2), 126.2(x2), 119.1, 63.5, -0.39(x3)。
Claims (4)
1. a kind of chiral platinum complex crystal, its chemical formula is as follows：
（Ⅰ）.
2. the chiral platinum complex crystal (I) described in claim 1, at a temperature of 293 (2) K, in Oxford X-ray monocrystalline
On diffractometer, with the CuK alpha rays through graphite monochromator monochromatization（λ=1.54184Å）Diffraction number is collected with ω-θ scan modes
According to, it is characterised in that crystal belongs to orthorhombic system, space group orthorhombic system, anorthic system, P212121；Cell parameter：a =
10.10222(13) Å α = 90°； b = 10.31601(18) Å β =90°；c = 19.4666(3) Å γ =90°.
3. the synthetic method of the chiral platinum complex crystal (I) described in claim 2, including synthesis and separate, weigh it is double-（4
(R)-isopropyl -4,5- dihydro -2- oxazolinyls）- acetonitrile zinc 0.2662g makes solvent dissolving of 30mL dichloromethane, then adds
Enter Pt（DMSO）2Cl2 0.3406g, at room temperature react 60 hours after stop reaction, filtering, add dichloromethane, petroleum ether and
Absolute ethyl alcohol, volatilize to obtain a kind of new platinum complex monocrystalline naturally.
4. the purposes of the chiral platinum complex crystal (I) described in claim 2, is henry of the complex crystal in ethyl pyruvate
Good catalytic performance is shown in profit reaction and the reaction of benzaldehyde and benzamide, its conversion ratio is up to 41%, 56% respectively
And 40%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710430760.XA CN107163085A (en) | 2017-06-09 | 2017-06-09 | A kind of preparation of chiral platinum complex crystal and purposes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710430760.XA CN107163085A (en) | 2017-06-09 | 2017-06-09 | A kind of preparation of chiral platinum complex crystal and purposes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107163085A true CN107163085A (en) | 2017-09-15 |
Family
ID=59825957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710430760.XA Pending CN107163085A (en) | 2017-06-09 | 2017-06-09 | A kind of preparation of chiral platinum complex crystal and purposes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107163085A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652205A (en) * | 2017-10-24 | 2018-02-02 | 合肥祥晨化工有限公司 | A kind of synthetic method and purposes of imines crystalline compounds |
| CN110448561A (en) * | 2019-08-08 | 2019-11-15 | 合肥工业大学 | A kind of purposes of chiral double oxazoline metal complexs |
| CN112480126A (en) * | 2020-12-11 | 2021-03-12 | 合肥工业大学 | Preparation and application of 5-alkyl quinazoline derivative |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327104A (en) * | 2014-10-12 | 2015-02-04 | 罗梅 | Allomorphic chiral zinc complex |
| CN105198935A (en) * | 2015-10-02 | 2015-12-30 | 合肥祥晨化工有限公司 | Chiral oxazoline palladium coordination compound |
-
2017
- 2017-06-09 CN CN201710430760.XA patent/CN107163085A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327104A (en) * | 2014-10-12 | 2015-02-04 | 罗梅 | Allomorphic chiral zinc complex |
| CN105198935A (en) * | 2015-10-02 | 2015-12-30 | 合肥祥晨化工有限公司 | Chiral oxazoline palladium coordination compound |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107652205A (en) * | 2017-10-24 | 2018-02-02 | 合肥祥晨化工有限公司 | A kind of synthetic method and purposes of imines crystalline compounds |
| CN110448561A (en) * | 2019-08-08 | 2019-11-15 | 合肥工业大学 | A kind of purposes of chiral double oxazoline metal complexs |
| CN112480126A (en) * | 2020-12-11 | 2021-03-12 | 合肥工业大学 | Preparation and application of 5-alkyl quinazoline derivative |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107163085A (en) | A kind of preparation of chiral platinum complex crystal and purposes | |
| Schuhknecht et al. | Isolation and properties of a palladium PBP pincer complex featuring an ambiphilic boryl site | |
| Ishida et al. | Synthesis of 3, 3-disubstituted α-tetralones by rhodium-catalysed reaction of 1-(2-haloaryl) cyclobutanols | |
| Wu et al. | Dansyl-based fluorescent chemosensors for selective responses of Cr (III) | |
| Rayati et al. | Electronic effects of substituents on the oxidation potentials of vanadyl complexes with tetradentate Schiff base ligands derived from 1, 2-propylenediamine | |
| Adao et al. | CuII–salan compounds: Synthesis, characterization and evaluation of their potential as oxidation catalysts | |
| Ahamed et al. | Thiomethoxychalcone-Functionalized ferrocene ligands as selective chemodosimeters for mercury (II): single-crystal X-ray structural signature of the [Hg8 (μ8-S)(SCH3) 12] 2+ cluster | |
| CN110423217A (en) | A kind of preparation method of conjugated enynes compound | |
| CN105001268A (en) | Chiral oxazoline platinum complex crystal and synthetic method thereof | |
| CN111995638B (en) | Synthesis method of 3-sulfur-1-glycal compounds | |
| US8338600B2 (en) | Copper-oxygen adduct complexes, and methods of making and use | |
| KR20110081697A (en) | Compounds having al(iii) ion selectivity and chemosensor using the same | |
| Wang et al. | Synthesis, structure and electrochemistry of new diferrocenyl pyridine derivatives | |
| Hirano et al. | Reactions of [RuCl 2 (NO)(terpy)]+(terpy= 2, 2′: 6′, 2 ″-terpyridine) with mono anions such as NO 2−, Br− and N 3−, and structural studies on terpyridineruthenium having a nitrosyl ligand | |
| Boixassa et al. | Reactivity of the ligand bis [2-(3, 5-dimethyl-1-pyrazolyl) ethyl] ether (L1) with Pd (II) and Pt (II): crystal structure of cis-[PtCl2 (L1)] | |
| CN106083505A (en) | A kind of method synthesizing β iodo nitroolefin compounds | |
| Elangovan et al. | First synthesis and electrogenerated chemiluminescence of novel p-substituted phenyl-2-quinolinylethynes | |
| Emandi et al. | Triptycene scaffolds: Synthesis and properties of triptycene-derived Schiff base compounds for the selective and sensitive detection of CN− and Cu2+ | |
| CN106188106A (en) | Zinc complex crystal | |
| CN109666006A (en) | Derivative connection thiazole compound of aryl and its preparation method and application | |
| Boixassa et al. | Synthesis and characterisation of pyrazolic palladium compounds containing alcohol functionality:: rotation around the Pd–N bond | |
| CN105237483B (en) | A kind of symmetric form pyrimidine radicals salt compounded of iodine and preparation method thereof | |
| Zheng et al. | Direct difluoromethylation of 2-arylidenindan-1, 3‑dione by photoredox-catalyzed radical addition | |
| EP3099658B1 (en) | Process of production of 2,3,6-trimethylphenol | |
| CN107382819A (en) | A kind of preparation method of 3 thioindole class compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170915 |
|
| RJ01 | Rejection of invention patent application after publication |