CN105001268A - Crystals of chiral oxazoline platinum complex and synthesize method of crystals - Google Patents
Crystals of chiral oxazoline platinum complex and synthesize method of crystals Download PDFInfo
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- CN105001268A CN105001268A CN201510492249.3A CN201510492249A CN105001268A CN 105001268 A CN105001268 A CN 105001268A CN 201510492249 A CN201510492249 A CN 201510492249A CN 105001268 A CN105001268 A CN 105001268A
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- platinum complex
- chiral oxazoline
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- oxazoline
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- -1 oxazoline platinum Chemical compound 0.000 title claims abstract description 17
- 239000013078 crystal Substances 0.000 title claims description 9
- 238000000034 method Methods 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- CHZCERSEMVWNHL-UHFFFAOYSA-N 2-hydroxybenzonitrile Chemical compound OC1=CC=CC=C1C#N CHZCERSEMVWNHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- STVVMTBJNDTZBF-SECBINFHSA-N (2r)-2-amino-3-phenylpropan-1-ol Chemical compound OC[C@H](N)CC1=CC=CC=C1 STVVMTBJNDTZBF-SECBINFHSA-N 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims abstract 2
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 229960001701 chloroform Drugs 0.000 claims 2
- 238000000605 extraction Methods 0.000 claims 2
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- QMXOFBXZEKTJIK-UHFFFAOYSA-N Glycinol Natural products C1=C(O)C=C2OCC3(O)C4=CC=C(O)C=C4OC3C2=C1 QMXOFBXZEKTJIK-UHFFFAOYSA-N 0.000 claims 1
- YQBZVSGMSMVIEC-UHFFFAOYSA-N [Co].O1C=NCC1 Chemical compound [Co].O1C=NCC1 YQBZVSGMSMVIEC-UHFFFAOYSA-N 0.000 claims 1
- 230000005260 alpha ray Effects 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical class O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000001556 precipitation Methods 0.000 claims 1
- 239000012047 saturated solution Substances 0.000 claims 1
- 125000006850 spacer group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 150000002825 nitriles Chemical class 0.000 abstract description 4
- 238000000926 separation method Methods 0.000 abstract description 3
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 abstract description 2
- 238000006842 Henry reaction Methods 0.000 abstract 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 26
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- HRGDZIGMBDGFTC-UHFFFAOYSA-N platinum(2+) Chemical compound [Pt+2] HRGDZIGMBDGFTC-UHFFFAOYSA-N 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 238000005712 Baylis-Hillman reaction Methods 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
- 229910018885 Pt—Au Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001414 amino alcohols Chemical class 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
- 239000013522 chelant Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 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
- 238000001514 detection method Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 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
- 239000011159 matrix material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000302 molecular modelling Methods 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000004424 polypyridyl Polymers 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 229940127224 quinoline drug Drugs 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- HYWCXWRMUZYRPH-UHFFFAOYSA-N trimethyl(prop-2-enyl)silane Chemical compound C[Si](C)(C)CC=C HYWCXWRMUZYRPH-UHFFFAOYSA-N 0.000 description 1
- LEIMLDGFXIOXMT-UHFFFAOYSA-N trimethylsilyl cyanide Chemical compound C[Si](C)(C)C#N LEIMLDGFXIOXMT-UHFFFAOYSA-N 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
-
- 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)
Abstract
The invention provides a chiral oxazoline platinum complex of the chemical formula (I) and a synthesize method of the chiral oxazoline platinum complex. The synthesize method comprises the following steps: taking platinum chloride relative to 39.8 mol% of 2-hydroxy-benzonitril as a catalyst; adding 9.64 mmol 2-hydroxy-benzonitril and 2.4897 g D-phenylalaninol; taking 50 mL chlorobenzene as a solvent; carrying out a reflux reaction for 60 hours; carrying out purification, that is, removing chlorobenzene after the reaction; carrying out column chromatography separation with methylene chloride and methanol between with the volume ratio is 1:1; carrying out natural volatilization to obtain monocrystals of the chiral oxazoline platinum complex. The chiral oxazoline platinum complex is relatively high in catalytic performance in a nitrile silicification reaction and a Henry reaction of benzaldehyde, and has the conversion rates of 92.5 % and 84.0 % in the nitrile silicification reaction and the Henry reaction respectively.
Description
one, technical field
The present invention relates to a kind of organometallic complex (title complex) and preparation method thereof, particularly nitrogenous oxazoline a metal-organic complex and preparation method thereof, is exactly a kind of platinum complex crystal and synthetic method thereof of chiral oxazoline.
two, background technology
Metal platinum complex to have caused the extensive concern of people because of it in the potential using value in anticancer and molecular magnet, fluorescent material etc.The synthetic method of metal platinum complex has many bibliographical informations 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。
three, summary of the invention
The present invention aims to provide a kind of Pt-N a metal-organic complex to be applied to catalytic field, and technical problem to be solved is selected Lin Qiang oxazolin as part and synthesized the platinum complex of chiral oxazoline.
The platinum complex of the chiral oxazoline alleged by the present invention is a kind of be by salicylonitrile, D-phenylalaninol and Tetrachloroplatinum prepare by the title complex shown in following chemical formula:
（Ⅰ）。
Chemical name: 2-[4(R)-benzyl-4,5-dihydro]-2-oxazolinyl } { (R)-1-hydroxyl-3-propyl phenyl 2-is amino } phenol platinum chloride title complex, is called for short title complex (I).
This title complex shows good catalytic performance in the nitrile silication and Henle reaction of phenyl aldehyde, and its transformation efficiency is respectively 92.5%, and 84.0%.
This synthetic method comprises synthesis and is separated, described synthesis makees catalyzer with relative to salicylonitrile 39.8 mol% platinum chloride, salicylonitrile 9.64 mmol, D-phenylalaninol 2.4897 g, makees solvent with 50mL chlorobenzene, back flow reaction 60 hours, purifying, namely reaction sloughs chlorobenzene after terminating, and by methylene dichloride/anhydrous methanol 1/1 column chromatography for separation by volume, volatilize to obtain chiral oxazoline platinum complex monocrystalline naturally.
Building-up reactions is as follows:
This synthetic method one step obtains target product, and technique is simple, easy to operate.
The reaction mechanism of this reaction can be speculated as reaction and first generate Lin Qiang oxazolin, two nitrogen-atoms of three chlorine atoms then in Tetrachloroplatinum and hydroxyl and chiral amino alcohol slough three salt acid molecules, and form this chiral coordination compound with the nitrogen-atoms coordination of oxazoline.
Four, accompanying drawing explanation
The X-diffraction analysis figure of Fig. 1 { 2-[4(R)-benzyl-4,5-dihydro]-2-oxazolinyl } { (R)-1-hydroxyl-3-propyl phenyl 2-is amino } phenol platinum chloride title complex.
Five, embodiment
In 100mL two-mouth bottle, add Tetrachloroplatinum 1.2952g (3.84 mmol), 50mL chlorobenzene, salicylonitrile 1.1483g (9.64mmol), D-phenylalaninol 2.4897 g, at high temperature reflux mixture 60h, stopped reaction, by methylene dichloride/anhydrous methanol 1/1 column chromatography for separation, volatilize to obtain chiral oxazoline platinum complex monocrystalline naturally, productive rate 68 %; M.p.:138-142 ° of C, [a]
5 d=-90.36 ° of (0.0332, CH
3oH), ultimate analysis: test value: C:47.32 %, H:4.03%, N:4.35%; Calculated value: 47.51%, 3.99%, N, 4.43%; IR (KBr): 3428,3201,3061,3027,2922,1620,1551,1495,1478,1454,1441,1405,1339,1239,1090,1030,1161,856,750. 701; Match crystal volume data is as follows:
Empirical formula C25H25ClN2O3 Pt
Molecular weight 632.01
Temperature 296 (2) K
Wavelength 0.71073
Crystallographic system, Space group Monoclinic system, P2 (1) P2 (1) P2 (1)
Unit cell parameters a=5.287 (3) α=90 °.
b = 18.919(11) ? β = 90 °.
c = 23.425(14) ? γ = 90 °.
Volume 2343(2)
Electric density 4,1.792 Mg/m^3
Absorption correction parameter 6.132 mm^-1
Number of electrons 1232 in unit cell
Crystallographic dimension 0.180 x 0.150x 0.120mm
The scope 1.739to 25.999 at Theta angle
Index capture range-the 6<=h<=6 of HKL ,-23<k<20 ,-28<l<=28
Collection/independent diffraction data 17118/ 4615 [R (int)=0.0525]
Data integrity degree 99.9 % of theta=30.5
The method Multi Slice Mode of absorption correction
Transmitance 0.7456 and 0.4216 of minimax
The Matrix least square method of the method F^2 that refine uses
Number/the number of parameters 4615/36/290 of data number/use restriction
The method 1.056 that refine uses
Consistence factor R 1=0.0369, the ω R2=0.0734 of point diffraction
Identical factor R 1=0.0482, ω R2=0.0773 of observable diffraction
Absolute configuration parameter 0.008(9)
Maximum summit on difference Fourier figure and peak valley 1.458 and-0.0706e. ^-3
the typical bond distance's data of crystal:
Pt(1)-N(1) 1.988(9)
Pt(1)-O(1) 1.999(8)
Pt(1)-N(2) 2.068(9)
Pt(1)-Cl(1) 2.286(3)
N(1)-C(7) 1.287(12)
N(1)-C(9) 1.497(12)
N(2)-C(18) 1.503(12)
O(1)-C(1) 1.334(13)
O(2)-C(7) 1.347(12)
O(2)-C(8) 1.443(12)
O(3)-C(17) 1.389(16)
O(3)-H(3) 0.8200
C(1)-C(6) 1.405(15)
C(1)-C(2) 1.418(14)
C(2)-C(3) 1.356(16)
C(2)-H(2) 0.9300
C(3)-C(4) 1.363(16)
C(3)-H(3A) 0.9300
C(4)-C(5) 1.353(15)
C(4)-H(4) 0.9300
C(5)-C(6) 1.420(15)
C(5)-H(5) 0.9300
C(6)-C(7) 1.437(14)
C(8)-C(9) 1.511(14)
C(8)-H(8A) 0.9700
C(8)-H(8B) 0.9700
C(9)-C(10) 1.524(13)
C(9)-H(9) 0.9800
C(10)-C(11) 1.510(17)
C(10)-H(10A) 0.9700
C(10)-H(10B) 0.9700
C(11)-C(12) 1.380(18)
C(11)-C(16) 1.39(2)
C(12)-C(13) 1.417(18)
C(12)-H(12) 0.9300
C(13)-C(14) 1.33(2)
C(13)-H(13) 0.9300
C(14)-C(15) 1.387(19)
C(14)-H(14) 0.9300
C(15)-C(16) 1.375(19)
C(15)-H(15) 0.9300
C(16)-H(16) 0.9300
C(17)-C(18) 1.520(15)
C(17)-H(17A) 0.9700
C(17)-H(17B) 0.9700
C(18)-C(19) 1.516(17)
C(18)-H(18) 0.9800
C(19)-C(20) 1.511(14)
C(19)-H(19A) 0.9700
C(19)-H(19B) 0.9700
C(20)-C(25) 1.336(16)
C(20)-C(21) 1.387(16)
C(21)-C(22) 1.379(15)
C(21)-H(21) 0.9300
C(22)-C(23) 1.313(17)
C(22)-H(22) 0.9300
C(23)-C(24) 1.366(18)
C(23)-H(23) 0.9300
C(24)-C(25) 1.390(17)
C(24)-H(24) 0.9300
C(25)-H(25) 0.9300
the typical bond angle data of crystal:
N(1)-Pt(1)-O(1) 91.0(3)
N(1)-Pt(1)-N(2) 176.4(4)
O(1)-Pt(1)-N(2) 88.0(3)
N(1)-Pt(1)-Cl(1) 94.7(3)
O(1)-Pt(1)-Cl(1) 174.3(2)
N(2)-Pt(1)-Cl(1) 86.3(3)
C(7)-N(1)-C(9) 108.2(9)
C(7)-N(1)-Pt(1) 125.1(7)
C(9)-N(1)-Pt(1) 126.7(6)
C(18)-N(2)-Pt(1) 120.5(7)
C(1)-O(1)-Pt(1) 123.7(6)
C(7)-O(2)-C(8) 106.6(8)
C(17)-O(3)-H(3) 109.5
O(1)-C(1)-C(6) 125.7(10)
O(1)-C(1)-C(2) 116.9(10)
C(6)-C(1)-C(2) 117.4(11)
C(3)-C(2)-C(1) 121.6(12)
C(3)-C(2)-H(2) 119.2
C(1)-C(2)-H(2) 119.2
C(2)-C(3)-C(4) 121.2(12)
C(2)-C(3)-H(3A) 119.4
C(4)-C(3)-H(3A) 119.4
C(5)-C(4)-C(3) 119.5(12)
C(5)-C(4)-H(4) 120.2
C(3)-C(4)-H(4) 120.2
C(4)-C(5)-C(6) 121.9(10)
C(4)-C(5)-H(5) 119.0
C(6)-C(5)-H(5) 119.0
C(1)-C(6)-C(5) 118.4(10)
C(1)-C(6)-C(7) 121.7(10)
C(5)-C(6)-C(7) 119.9(10)
N(1)-C(7)-O(2) 116.3(9)
N(1)-C(7)-C(6) 127.6(10)
O(2)-C(7)-C(6) 116.0(9)
O(2)-C(8)-C(9) 106.2(8)
O(2)-C(8)-H(8A) 110.5
C(9)-C(8)-H(8A) 110.5
O(2)-C(8)-H(8B) 110.5
C(9)-C(8)-H(8B) 110.5
H(8A)-C(8)-H(8B) 108.7
N(1)-C(9)-C(8) 102.3(8)
N(1)-C(9)-C(10) 112.0(8)
C(8)-C(9)-C(10) 113.7(9)
N(1)-C(9)-H(9) 109.5
C(8)-C(9)-H(9) 109.5
C(10)-C(9)-H(9) 109.5
C(11)-C(10)-C(9) 108.1(9)
C(11)-C(10)-H(10A) 110.1
C(9)-C(10)-H(10A) 110.1
C(11)-C(10)-H(10B) 110.1
C(9)-C(10)-H(10B) 110.1
H(10A)-C(10)-H(10B) 108.4
C(12)-C(11)-C(16) 118.2(14)
C(12)-C(11)-C(10) 122.6(13)
C(16)-C(11)-C(10) 119.2(12)
C(11)-C(12)-C(13) 121.0(15)
C(11)-C(12)-H(12) 119.5
C(13)-C(12)-H(12) 119.5
C(14)-C(13)-C(12) 118.3(15)
C(14)-C(13)-H(13) 120.8
C(12)-C(13)-H(13) 120.8
C(13)-C(14)-C(15) 122.3(15)
C(13)-C(14)-H(14) 118.8
C(15)-C(14)-H(14) 118.8
C(16)-C(15)-C(14) 119.3(16)
C(16)-C(15)-H(15) 120.3
C(14)-C(15)-H(15) 120.3
C(15)-C(16)-C(11) 120.5(16)
C(15)-C(16)-H(16) 119.8
C(11)-C(16)-H(16) 119.8
O(3)-C(17)-C(18) 112.6(11)
O(3)-C(17)-H(17A) 109.1
C(18)-C(17)-H(17A) 109.1
O(3)-C(17)-H(17B) 109.1
C(18)-C(17)-H(17B) 109.1
H(17A)-C(17)-H(17B) 107.8
N(2)-C(18)-C(19) 111.0(10)
N(2)-C(18)-C(17) 109.7(8)
C(19)-C(18)-C(17) 113.8(10)
N(2)-C(18)-H(18) 107.4
C(19)-C(18)-H(18) 107.4
C(17)-C(18)-H(18) 107.4
C(20)-C(19)-C(18) 111.9(9)
C(20)-C(19)-H(19A) 109.2
C(18)-C(19)-H(19A) 109.2
C(20)-C(19)-H(19B) 109.2
C(18)-C(19)-H(19B) 109.2
H(19A)-C(19)-H(19B) 107.9
C(25)-C(20)-C(21) 117.0(10)
C(25)-C(20)-C(19) 122.3(11)
C(21)-C(20)-C(19) 120.7(11)
C(22)-C(21)-C(20) 121.0(12)
C(22)-C(21)-H(21) 119.5
C(20)-C(21)-H(21) 119.5
C(23)-C(22)-C(21) 120.4(12)
C(23)-C(22)-H(22) 119.8
C(21)-C(22)-H(22) 119.8
C(22)-C(23)-C(24) 120.9(12)
C(22)-C(23)-H(23) 119.6
C(24)-C(23)-H(23) 119.6
C(23)-C(24)-C(25) 118.4(13)
C(23)-C(24)-H(24) 120.8
C(25)-C(24)-H(24) 120.8
C(20)-C(25)-C(24) 122.4(13)
C(20)-C(25)-H(25) 118.8
C(24)-C(25)-H(25) 118.8
(3), nitrile silicification reaction application
2-phenyl-2-(three silyloxy) propionitrile
0.2mmol title complex I; phenyl aldehyde 0.1mL; TMSCN 0.3 ml (3.3mmol); 2mL anhydrous methanol; in succession add under 30 ~ 35 C, after 40 hours, add shrend and to go out (sherwood oil/methylene dichloride: 5/1) after post layer; obtain colourless oil liquid, transformation efficiency: 92.5 %;
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).
(4), Henle reaction application
The title complex I(catalytic amount of getting 0.20mmol is 20%) in the little flask of 25mL, add the absolute methanol solution of 2 milliliters, then, the phenyl aldehyde of 0.1mL and the Nitromethane 99Min. of 0.5mL is added in above-mentioned solution, stirring at room temperature, react after 40 hours, carry out nmr analysis, transformation efficiency: 84.0 %;
1h NMR (300MHz, CDCl
3) 7.28 ~ 7.32 (m, 5H, Ar-H), 5.32 ~ 5.35 (d, J=9.18Hz, 1H ,-CH), 4.38 ~ 4.56 (m, 2H ,-CH
2), 3.89 (br, 1H ,-OH).
(5), allyl group alkylated reaction application
The title complex I(catalytic amount of getting 0.20mmol is 20%) in the little flask of 25mL, add the dichloromethane solution of 2 milliliters, then, the phenyl aldehyde of 0.1mL and the allyl trimethyl silane of 0.3mL is added in above-mentioned solution, stirring at normal temperature, react after 48 hours, carry out nmr analysis, transformation efficiency: 42%;
1h NMR (300MHz, CDCl
3) 7.27 ~ 7.33 (m, 5H, Ar-H), 5.79 ~ 5.80 (m, 1H), 5.12 ~ 5.17 (m, 2H ,-CH
2), 4.71(d, J=5Hz, 1H), 2.49 ~ 2.50 (m, 2H), 2.28(s, 1H);
(6) Baylis-Hillman reactive applications
The title complex I(catalytic amount of getting 0.20mmol is 20%) in the little flask of 25mL, add the dichloromethane solution of 2 milliliters, then; in above-mentioned solution, add phenyl aldehyde and the 0.5mL methyl acrylate of 0.1mL, stirring at normal temperature, react after 48 hours; carry out nmr analysis, transformation efficiency: 53%;
1hNMR (300MHz, CDCl
3) 7.20 ~ 7.41 (m, 5H, Ar-H), 6.30 (s, 1H), 5.45 (s, 1H), 3.70 (s, 3H), 3.15 (s, 1H).
Claims (3)
1. a chiral oxazoline platinum complex, is characterized in that: prepared by salicylonitrile, D-phenylalaninol and Tetrachloroplatinum, by the title complex shown in following chemical formula (I):
（Ⅰ）。
2. chiral oxazoline platinum complex (I) according to claim 1, at 296 (2) K temperature, on the X-ray single crystal diffraction instrument of Oxford, diffraction data is collected with ω-θ scan mode with the MoK alpha-ray (λ=0.71073) through graphite monochromator monochromatization, it is characterized in that crystal belongs to rhombic system, spacer P2 (1) 2 (1) 2 (1), unit cell parameters: a=5.287 (3) α=90 °; B=18.919 (11) β=90 °; C=23.425 (14) γ=90 °.
3. the synthetic method of chiral oxazoline platinum complex (I) according to claim 1, comprise synthesis and be separated, described synthesis 50.0 mol% cobalt chloride hexahydrates make catalyzer, salicylonitrile 20.0 mmol, D-benzene glycinol 4.4391 g, solvent is made with 50mL chlorobenzene, back flow reaction 72 hours, purifying, namely reaction sloughs chlorobenzene after terminating, with chloroform extraction after being dissolved in water, with column chromatography purification after extraction phase precipitation; With trichloromethane/ethanol preparation saturated solution, volatilize to obtain chiral oxazoline cobalt complex monocrystal naturally.
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| CN105237579A (en) * | 2015-11-18 | 2016-01-13 | 罗梅 | Platinum complex crystal |
| CN107337652A (en) * | 2017-07-05 | 2017-11-10 | 合肥祥晨化工有限公司 | A kind of Chiral oxazoline cobalt complex and purposes |
| CN110305167A (en) * | 2019-06-18 | 2019-10-08 | 合肥工业大学 | A kind of preparation and purposes of chirality platinum complex |
| CN110314165A (en) * | 2019-07-16 | 2019-10-11 | 合肥工业大学 | A kind of purposes of chirality oxazoline palladium complex crystal |
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