SU555103A1 - Coordination compounds of lanthanides with fluorinated -diketone as a lanthanide shift agent for mp spectroscopy - Google Patents

Description

(54) COORDINATION CONNECTIONS OF LANTHANIDES

WITH FLUORINATED (3-DICETON AS AN ANT ANIDE SHIFT REAGENT FOR NMR SPECTROSCONY), the properties were checked by measuring the paramagnetic shifts of the proton A, B or C signals in the NMR spectra of the replica replicator in a replica replica reject piece. 3 in the №) l rn ratio equal to 0.3 (where Cg 5

Shear reagent

The magnitudes of the proton signal shifts, Hz, the concentration of the shift reagent, Cc is the concentration of ethyl acetate, mol / l). The table shows the magnitudes of paramagnetic shifts D6, caused by the shift reagents in the NMR spectrum of ethyl acetate.

and (SNE) zS-S (0) SNS (o) SG20SGz

Claims (2)

(0) SG2, EiM). The table shows the magnitudes of paramagnetic shifts in the spectrum of their NMR of ethyl acetate with Eu (fod) 3 added to it under the same conditions (at a molar ratio of Cg / Cg of 0.3). From the above data it can be seen that the change in the magnitudes of paramagnetic shifts, caused by the addition of the complexes presented on the test complex to Her (p-di ket) 3, is greater than when she was fed (A) 3. The advantage of n {hdag.h. in front of Her (fod) 3 is also their lower hygroscopicity. So the combination of EU | rj-c (o} cHC | 0bcF2 iDpls SV g when stored in air for 24 hours does not change its color, while Her (fod) s after holding it in air for 1-2 hours and: The color is yellow to white, indicating water addition. The proposed compounds are highly soluble in the floor and non-polar solvents. Therefore, representatives of newly synthesized compounds have better shear characteristics and less hygroscopicity compared to Ln shear reagents (fod ) 3. These compounds can be used These methods are used as lanthanide shear reagents for NMR spectroscopy to study the structure of organic molecules, including biological objects, to emit their conformations, to determine the binding sites of metal ions with polyfunctional molecules, to study the kinetics of ligand exchange, etc. Suggested The compounds are prepared according to a method based on known reactions. The synthesis is as follows: To a water-alcohol solution of lanthanide nitrate (solution No. 1) is added with a vigorous process. Shivani alcoholic solution | 3-diketonate sodium (№2 solution). The latter is obtained by neutralizing the alcohol solution of the corresponding 3-diketone with a water, but alcohol solution of NaOH. To isolate the complexes in solid form, an alcoholic solution containing Lp (P-diket) 3 and sodium nitrate with vigorous stirring are poured into a large volume of distilled water (tenfold excess relative to the volume of the alcohol solution) cooled to 5 ° C. the product is separated from water and purified by reprecipitation from n-hexane or n-octane, followed by sublimation in vacuo and substance. Example. To 20 ml of a 0.25 M methanol solution of Eu (MO3) from the SHjO brand CHP (solution no. 1), under stirring with a magnetic displacer, 20 ml of a 0.75 M solution / 3-sodium diketonate in methanol (solution) are added, where is diketone 2, 2 - dimethyl - 6 - trifluoromethoxy - 6,6 - difluorohexanedione-3, 5 (cn) 3C-cc, -c-crgOCF. II 11 o o At the same time, sodium nitrate precipitates from the solution. With vigorous stirring, the mixture obtained is poured into 400 ml of distilled water, cooled beforehand to 5 ° C. The solution is moved. 2h The amorphous precipitate that forms is filtered and dried in air. The yield of the crude product is 85% of the theoretical. The creepous precipitate is precipitated from n-hexane, sublimated under a vacuum, dried in a vacuum desiccator for 2-4 hours. The dried product is greenish-yellow in color. Found,%: C 34.43; H3.53; It is 16.20 ° C27H3oFl509Eu Calculated,%: C 34.66; H 3.21; It is 16.25% P r and M e r 2. To 20 ml of a 0.25 M solution of Eu (MO3) s SHjO in methanol (solution No. 1), 20 ml of a 0.75 M methanol solution of | 3-diketonate are added with magnetic stirring sodium (solution No. 2), where | 3-diketone-1- (ofetenyl) - 4 (a-perfluorotetrahydrofuryl) -4, 4-α-dafluorobutanedione-1,3-Further, proceed as in Example 1. The yield of the crude product is 72%. The compound is not sublimated. It is purified by reprecipitation from n-octane, its solution is at room temperature and then cooled to 0 ° C, dried in 5 vacuum desiccator over P20s for 2-4 hours. The dried product is bright yellow. Found,%: C 32.11; H 1.0; Fu 11.20. CaeHiiEuFzTOsSs Calculated,%: C 32.0; H 0.9; Eu 11.27 .y Prize. To 20 ml of a 0.25 M solution of Yb (MO3) s in methanol (solution No. 1), with stirring with a magnetic stirrer, add 20 ml of a 0.75 M solution of sodium 3-diketonate in methanol (solution No. 2), where | 3 - diketone-1 - (a-thiyyush) i -a-4- (ag-perfluoro tetrahydrofuryl) -4,4-difluorobutanedione-1, 3. Next, proceed as in Example 1. The precipitate in the form of a viscous oil is separated from the solution, washed with distilled water and dried in a drying oven at 110 ° C for 2 hours. 20 Crude product yield 75%. The compound is not sublimated. It is purified by reprecipitation from n-octane, its solution is at room temperature and then cooled to 0 ° C, dried in a vacuum desiccator over Pa0s for 2-4 hours. Dried yellow 25 product. Found,%: C 31.67; H 1.11; Yb 12.60 C, eH, 0, Fj., S3Yb Calculated,%: C 31.53; H 0.87; Vb 12.62. Example 4. 20 ml of a 0.75 M solution (sodium 3-diketonate in methanol (solution No. 2) are added with a magnetic stirrer to 20 ml of a 0.25 M solution of EO Eu (LO3) s6H20 in methanol (solution 1)). where (-diketone-1-phenyl-4- (aperfortetrahydrofuryl) -4,4-difluorobutanedione-85 1.3. Next, proceed as in Example 1. The precipitate as a viscous oil is separated from the solution, washed with distilled water and dried in a drying oven. cabinet at 110 ° C for 2 hours, the crude product exiting 73%. Cleaned with a single precipitate by precipitating from n-octane, dissolved at room temperature and cooling. then about 0 ° C, dried in a vacuum desiccator for 2-4 hours, Dried bright yellow vet. Found: C 37.84; H 1.45; She 11.50 C42H, 8EUF2709 Calculated,% : C, 37.85; H, 1.35; Her, 11.49. Claims of the invention. Coordination compounds of lanthanides with thoriated | 3-diketone of the general formula (where Lp is europium or ytterbium. CH3 K.- | -C-Cis b aryl or thiophenyl ; 2. F-I-CF OCFj-CF CF OCFj -CF Tj, as a lanthanide shift agent for NMR spectroscopy.