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Scheme .I. Cyclopolladation reactions of ligand (L)

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Ɂɚ ɩɨɫɥɟɞɧɢɟ ɝɨɞɵ ɜɵɩɭɳɟɧɨ ɛɨɥɶɲɨɟ ɤɨɥɢɱɟɫɬɜɨ ɤɧɢɝ ɢ ɨɛɡɨɪɨɜ ɩɨ ɨɪ ɝɚɧɢɱɟɫɤɨɣ ɷɥɟɤɬɪɨɧɢɤɟ ɩɚɬɟɧɬɭɟɬɫɹ ɜɫɺ ɛɨɥɶɲɟɟ ɤɨɥɢɱɟɫɬɜɨ ɫɨɟɞɢɧɟɧ ɢɣ ɢ ɭɫɬɪɨɣɫɬɜ ɧɚ ɨɫɧɨɜɟ ɨɪɝɚɧɢɱɟɫɤɢɯ ɦɚɬɟɪɢɚɥɨɜ. Ɉɝɪɨɦɧɵɟ ɭɫɩɟɯɢ ɜ ɫɢɧɬɟɡɟ ɫɨɩɪɹɠɺɧɧɵɯ ɩɨɥɢɦɟɪɨɜ ɢ ɨɥɢɝɨɦɟɪɨɜ ɧɟ ɫɦ ɨɝɥɢ ɛɵ ɛɵɬɶ ɞɨɫɬɢɝɧɭɬɵ ɛɟɡ ɭɫɩɟɯɨɜ ɨɪɝɚɧɢɱɟɫɤɨɣ ɯɢɦɢɢ ɜ ɨɛɥɚɫɬɢ ɦɟ ɬɚɥɥɨɪɝɚɧɢɱɟɫɤɨɝɨ ɤɚɬɚɥɢɡɚ ɧɚ ɨɫɧɨɜɟ ɤɨɦɩɥɟɤɫɨɜ ɩɟɪɟɯɨɞɧɵɯ ɦɟɬɚɥɥɨ ɜ. Ⱥɧɚɥɢɡ ɪɟɡɭɥɶɬɚɬɨɜ ɢɫɫɥɟɞɨɜɚɧɢɣ ɩɨɤɚɡɚɥ, ɱɬɨ ɧɚ ɜɵɯɨɞɵ ɮɭɧɤɰɢɨɧɚɥ ɢɡɢɪɨɜɚɧɧɵɯ ɝɥɢɤɨɥɶɭɪɢɥɨɜ ɨɤɚɡɵɜɚɟɬ ɜɥɢɹɧɢɟ ɯɚɪɚɤɬɟɪ ɡɚɦɟɳɟɧɢɹ ɭ ɚ ɬɨɦɨɜ ɚɡɨɬɚ ɢ ɚɬɨɦɨɜ ɭɝɥɟɪɨɞɚ ɋ(4) ɢ ɋ(5) ȾȽɂ 1ɚ-ɫ ɢ ɪɚɡɜɟɬɜɥɟɧɢɹ ɚɥɤɢɥɶɧ ɨɣ ɰɟɩɢ ɜ ɦɨɱɟɜɢɧɚɯ 3 ɢ 6, ɤɨɥɢɱɟɫɬɜɚ ɤɢɫɥɨɬɵ ɢ.

Ƚɥɢɤɨɥɶɭɪɢɥɵ 8a-e ɩɨɥɭɱɚɸɬ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ 0.5 ɦɨɥɟɫɧ ɥɚ 9ɚ-ɫ ɢɫɩɨɥɶɡɭɸɬ 2.5 ɦɦɨɥɹ HCl ɞɥɹ 9d (83%), ɩɟɪɢɞ ɤɪɢɫɬɚɥɥɢ ɡɭɸɬɫɹ ɜ ɜɢɞɟ ɫɨɥɶɜɚɬɚ ɫ ɦɨɥɟɤɭɥɨɣ ɦɟɬɚɧɨɚ ɚɨɨ ɦɟɬɚɧɨɨd. Ɋɟɚɤɰɢɢ ȾȽɂ 4b ɫ (S)-N-ɤɚɪɛɚɦɨɢɥɧɨɪɜɚɥɢɧɨɦ 12c ɜ ɩɪɢɫɭɢɢɫɢl ɂ 4d ɫ N-ɤɚɪɛɚɦɨɢɥ-Į-ɚɦɢɧɨɦɚɫɥɹɧɣ ɤɢɫɥɨɬɨɣ 12b ɜ ɩɪɢɫe, ɬHCl ɤ 1 Ⱦɥɹ ɨɰɟɧɤɢ ɨɩɬɢɱɟɫɤɨɣ ɱɢɫɬɨɬɵ ɷɧɚɧɬɢɨɦɟɪɨɨɜ 3-ɚɦɢɪɨɨɤ ɚɡɪɚɛɨɬɚɧɵ ɦɟɬɨɞɵ ɫ ɩɨɦɨɳɶɸ ȼɗɀɏ ɧɚ ɞɢɪɚɟɩɧ ɡɚɚɯ (ɫ ɩɪɟɞɜɪɢɢɬ (5) [5]

Kinetic resolution of 1-methyl- and 1-phenyl-3-amino-1,2-dicarba-closo-dodecaboranes by acylation with chiral acyl chlorides // Mendeleev Commun. - ɢɠɧɵɯ ɮɚɡɚɯ // ɂɡɜ .

- ɨɮɭɪɚɡɚɧɨɜ.

This study reports on the synthesis of a new family of organopalladium complexes by cyclometalation of the heterocyclic ligand (L). Antimicrobial screening of the ligand and complexes showed that the acetate bridge complex has higher activity than other compounds. All the complexes show weak multiple bands in the range 3000-2840cm-1 due to aromatic and aliphatic stretches.

The shift of the C = N stretch to lower wavenumber compared to that (1600 cm-1) of the free Schiff base is expected due to the N-coordination of the azomethine in all complexes(16). All the orthopalladate species show strong bands in the range (770-750 cm-1) which are characteristic of the out-of-plane (C-H) bond of the ortho-substituted aromatic ring(18), giving good evidence for the electrophonic substitution of the ortho-hydrogen by Pd, which is also confirmed by the appearance of a weak band in the range 590-580cm-1 due to ȞPd-c(19). The 1H NMR spectrum of complex (1) showed the presence of a broadened unresolved pattern in the aromatic region that could explain the folded open book shape structure of the complex.

On the other hand, the 1H NMR spectrum of complex (3) shows the absence of signals in the range ±1.8-2.23 ppm, indicating the fully metathetical reaction of the acetate groups by the bromide. Orthometallation is supported by the study of the 1H NMR spectra of the free ligand and its palladium complexes. The magnetic measurements and the electronic spectral data indicate the square, planar geometric structure of all cyclopalladate complexes (22).

Antimicrobial activity of the Schiff base (L) and its cyclopalladate complexes was tested by the disc diffusion method (24).

Table 1: Elemental analysis, colors and melting points of ligand (L) and its  complexes
Table 1: Elemental analysis, colors and melting points of ligand (L) and its complexes

2-ɨɤɫɚɡɨɥɢɧɨɜ

Many tetrahydrothiopyrans have been obtained by the interaction of ketones with formaldehyde and sodium methanethiolate or/and sodium sulfide, some of their transformations have been described. Chelation of Cu(II) with ethyleneamines is used for a rapid and simple spectrophotometric method for the determination of NH-groups in ethyleneamines. , - ɤɚɡɚɥ ɫɟɛɹ ɩɟ ɪɫɩɟɤɬɢɜɧɵɦ ɷɤɫɬɪɚɝɟɧɬɨɦ ɰɜɟɬɧɵɯ ɢ ɛɥɚɝɨɪɨɞɧɵɯ ɦɟɬɚɥɥɨɜ.

- ɚɦɢɞɨɜ ɩɨɹɜɥɹɸɬɫɹ ɭɲɢɪɟɧɧɵɟ ɢɧɬɟɧɫɚɜɧɵɟ ɢɢɦɦɪɶɶɶɶɲ ɢ ɭɞɟɪɠɢɜɚɧɢɹ. - ɨɟɞɢɧɟɧɢɢ 3- ȺɌ ɬɢɬɪɭɟɬɫɹ ɬɨɥɶɤɨ 1 ɚɡɨɬ. - - ~2853 ɫɦ-1.

Ɍɚɤɢɦ ɨɛɪɚɡɨɦ, ɞɥɹ ɢɞɟɧɬɢɮɢɤɚɰɢɢ ɷɬɢɥɟɧɚɦɢɧɨɜ, ɚɰɢɥɢɪɨɜɚɧɠɯ Ú,Į'-ɪɚ ɡɜɟɬɜɥɟɧɵɦɢ ɤɚɪɛɨɧɨɜɦɢ ɤɢɫɥɨɬɦɚɢ ɋ10-14, ɧɚɢɛɨɥɟɟ ɭɞɨɛɧɨ ɢɫɩɨɥɶɡɨɜɚɬ ɶ ɫɥɚɛɨɩɨɥɶɧɵɟ ɫɢɧɝɥɟɬɧɵɟ ɫɢɝɧɚɥɵ, ɯɚɪɚɤɬɟɪɢɡɭɸɳɢɟ ɬɟɪ- ɦɢɧɚɥɶɧɵɟ ɢ ɜɧɭɬɪɟɧɧɢɟ ɚɦɢɞɧɵɟ ɝɪɭɩɩɵ.

9 NPh CO 2 Me

Ɉɞɧɢɦ ɢɡ ɬɚɤɢɯ ɨɛɳɢɯ ɫɢɧɬɟɬɢɱɟɫɤɢɯ ɩɨɞɯɨɞɨɜ ɤ ɩɨɥɭɱɟɧɢɸ ɤɨɧɞɟɧɫɢɪ ɨɜɚɧɧɵɯ ɫ ɚɪɨɦɚɬɢɱɟɫɤɢɦ ɚɡɨɰɢɧɨ ɨɠɟɬ ɫɬɬɚɶ ɜɩɟɪɜɜ ɵɟ ɨɩɢɫɚɧɧɚɹ ɧɚɦɢ ɪɟɚɤɰɢɹ ɪɚɫɲɢɪɟɧɢɹ ɬɟɬɪɚɝɢɞɪɨɩɢɪɢɞɢɧɨɜɨɝɨ ɚɡɨɰɢɧɨɜɨɝɨ ɢ ɬɟɬɪɚɝɢɞɪ ɨɚɡɟɩɢɧɨɜɨɝɨ ɤɨɥɶɰɚ ɞɟɣɫɬɜɢɟɦ ɚɥɤɢɧɨɜ ɚɤɬɢɜɢɪɨɜɚɧɧɵɯ ɷɥɟɤɬɪɨɧɨɚɤɰ ɟɩɬɨɪɧɵɦɢ ɡɚɦɟɫɬɢɬɟɥɹɦɢ. Ȼɵɥɨ ɩɨɤɚɡɚɧɨ, ɱɬɨ ɬɪɚɧɫɮɨɪɦɚɰɢɹ ɬɟɬɪɚɝɢɞɪɨɩɢɪɢɞɨɩɢɪɢɦɢɞɢɧɨɜ 10, 11 ɟɪɦɢɧɚɥɶɧɵɯ ɚɥɤɢɧɨɜ ɫɜɹɡɚɧɚ ɫ Ƚɨɮɦɚɧɨɜɫɤɢɦ ɪɚɫɳɟɩɥɟɧɢɟɦ ɬɟɬɪɚɝɢɞɪ ɨɩɢɪɢɞɢɧɨɜɨɝɨ ɤɨɥɶɰɚ, ɱɬɨ ɩɪɢɜɨɞɢɬ ɟɧɧɵɯ ɩɢɪɢɦɢɞɢɧɨɜ 12,13. - ɞɧɵɟ 5-ɨɤɫɨɩɪɨɥɢɧɚ (ɩɢɪɨɝɥɭɬɚɦɢɧɨɜɨɣ ɤɢɫɥɨɬɵ) ɡɨɜɚɧɢɟɦ ɩɪɨɢɡɜɨɞɧɵɯ ɝɥɭɬɚɦɢɧɨɜɨɣ ɤɢɫɥɨɬɵ.

إɧɚɥɢɡ ɥɢɬɟɪɚɬɪɪɧɵɯ ɞɚɧɧɵɯ ɩɨɤɚɡɚɥ, ɱɬɨ ɞɥɹ ɋ(4)-ɩɪɨɢɢ ɢɧɨɜɨɵ ɫɨ ɫɜɨɛɨɞɧɨɣ ɤɚɪɛɨɤɫɢɥɶɧɵɦɢ ɢ α-ɚɦɢɧɨɝɪɭɩɩɨɟɟ ɟɫɢɹ «ɨɬɤɪɵɬɨɰɟɩɧɚɹ ɮɨɪɦɚ – ɥɚɤɬɚɦ» ɫɭɳɟɫɬɜɟɧɧɨ ɟɞɵ. Ʉɚɤ ɜɢɞɧɨ ɢɡ ɩɪɟɞɫɬɚɜɥɟɧɧɨɣ ɬɚɛɥɢɰɵ, ɧɚɢɛɨɥɟɟ ɹɜɧɨɟ ɧɟ ɧɢɢ ɢɫɯɨɞɧɵɦ ɬɟɪɩɟɧɨɮɟɧɨɥɨɦ) ɪɟɝɢɫɬɪɢɪɨɞɧɵɦ ɬɟɪɩɟɧɨɮɟɧɨɥɨɦ) ɞɟ ɧɢɟ ɤɨɬɨɪɨɝɨ ɩɪɢɜɨɞɢɬ ɤ 15%-ɨɦɭ ɢɧɝɢɛɢɪɨɜɚɧɢɢɪɨɜɚɧɢɢɪɨɜɚɧɢɨɨɫɫɧɚ ɨɩɵ ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ ɤɨɧɬɪɨɥɸ. Ɋɚɧɟɟ ɛɵɥɨ ɭɫɬɚɧɨɜɥɟɧɨ, ɱɬɨ ɜɡɚɢɦɨɞɟɣɫɬɜɢɟ ɦɫɢɪɨɫɨ ɟ ɫɶɸ ɚɪɨɦɚɬɢɱɟɫɤɤɨɝɨ ɚɥɶɞɟɟɝɞɚ ɢ 5-ɚɦɢɨɨɬɟɬɪɚɧɨɬɟɬɪɚɧɨɬɟɬɪɚɡɨɥɢɢɢɢɧ . ɤɢɯ ɫɢɫɬ ɟɦ [1,2,3

Ɍɚɤ, ɦɟɬɢɥɨɜɵɟ ɷɮɢɪɵ ɚɰɢɥɩɢɪɨɜɢɧɨɝɪɚɞɧɵɯ ɤɢɫɥɨɬ ɪɟɚɝɢɪɭɸɬ ɫɨ ɫɦɟɫ ɶɸ ɚɪɨɦɚɬɢɱɟɫɤɨɝɨ ɚɥɶɞɟɝɢɞɚ ɢ 3-ɚɦɢɧɨ-1,2,4-ɬɪɢɚɡɨɥɚ ɫ ɨɛɪɚɡɨɜɚɧɢɟɦ 4-ɚ ɪ ɢɥ-3-ɚɰɢɥ2-ɦɟɬɨɤɫɢɤɚɪɛɨɧɢɥ-1,4-ɞɢɝɢɞɪɨɩɢɪɢɦɢɞɢɧɨ [1,2-d]ɬɪɢɚɡɨɥɚ [2 ]. Ɉɬɦɟɱɟɧɨ, ɱɬɨ 3-ɚɪɢɥɝɢɞɪɚɡɨɧɨ-3ɇ-ɮɭɪɚɧ-2-ɨɧɵ ɥɟɝɤɨ ɜɫɬɭɩɚɸɬ ɜ ɪɟɚɤɰɢɸ ɫ ɞɢɚɦɢɧɚɦɢ ɚɪɨɦɚɬɢɱɟɫɤɨɝɨ ɪɹɞɚ, ɫɬɪɭɤɬɭɪɚ ɩɪɨɞɭɤɬɨɜ ɢ ɧɚɩɪɚɜɥɟɧɢɟ ɦɨɞɢɮɢɤɚɰɢɢ ɡɚɜɢɫɢɬ ɨɬ ɯɚɪɚɤɬɟɪɚ ɢɫɩɨɥɶɡɭɟɦɵɯ ɞɢɚɦɢɧɨɜ. Ɍɪɟɯɤɨɦɩɨɧɟɧɬɧɚɹ ɪɟɚɤɰɢɹ ɦɟɬɢɥɨɜɵɯ ɷɮɢɪɨɜ ɚɰɢɥɩɢɪɨɜɢɧɨɝɪɚɞɧɵɯ ɤɢ ɫɥɨɬ ɫɨ ɫɦɟɫɶɸ ɚɪɨɦɚɬɢɱɟɫɤɨɝɨ ɢɥɢ ɝɟɬɟɪɨɰɢɤɥɢɱɟɫɤɨɝɨ ɚɥɶɞɟɝɢɞɚ ɢ ɚ 1.5-ɞɢɚɪɢɥ (ɝɟɬɟɪɢɥ) -4-ɚɰɢɥ-3-ɝɢɞɪɨɤɫɢ-3- ɩɢɪɪɨɥɢɧ-2-ɨɧɵ.

te ɫɥɨɬ ɫɨ ɫɦɟɫɶɸ ɚɪɨɦɚɬɢɱɟɫɤɨɝɨ ɚɥɶɞɝɞɟ ɢ ɚɦɢɞɚ ɝɨɨɤɫɨɠɨɨɨɨɨɠ ɚɬɶ ɤɚɨ 1-ɚɦɢɧɨ-5-4-3-2 ɟɪɚɡɢɧ -2,6-ɞɢɨɧɵ [9].

Ɇɨɧɨɷɬɚɧɨɥɚɦɢɧ 82

- ɹɜɥɹɸɳɢɯɫɹ ɜɵ ɫɨɤɨɪɟɚɤɰɢɨɧɧɨɫɩɨɫɨɛɧɵɦɢ ɫɨɟɞɢɧɟɧɢɹɦɢ ɩɨɡɜɨɥɹɸɳɢɦɢ ɩɨɥɭɱɢɬɶ ɧɚ ɫɜ ɨɟɣ ɫɧɗɨɟ ɪɚɡɥɢɱɧɵɟ ɚɰɢɤɥɢɱɟɫɤɢɟ ɢ ɝɟɬɟɪɨɨɰɢ ɤɥɢɱɟɫɤɢɟ ɫɨɟɞɢɧɟɧɢɹ, ɨɛɥɚɞɚɸɳɢɟ ɛɢɨɥɨɝɢɱɟɫɤɨɣ ɚɤɬɢɜɧɨɫɬɶɸ[2]. Ɉɛɧɚɪɭɠɟɧɨ ɡɧɚɱɢɬɟɥɶɧɨɟ ɩɨɜɵɲɟɧɢɟ ɪɚɫɬɜɨɪɢɦɨɫɬɢ ɥɟɤɚɪɫɬɜɟɧɧɵɯ ɫɭ ɛɫɬɚɧɰɢɣ ɢɡ ɩɨɥɭɱɟɧɧɢɣ ɡɚ ɫɱɟɬ ɨɛɪɚɚɜɨɚɧɢɡ ɜɨɞɨɪɚɚ ɫɬɜɨɪɢɦ ɵɯ ɤɨɦɩɥɟɤɫɨɜ ɥɟɤɚɪɫɬɜɟɧɧɵɯ ɜɟɳɟɫɬɜ ɫ ɩɪɢɦɟɧɟɧɧɵɦɢ ɤɨɦɩɥɟɤɫɨɨɛɪɚɡ ɨɜɚɬɟɥɹɦɢ. The structure of the newly synthesized substances was clarified using spectral (IR, NMR 1H, 13C).

Ʉɨɧɞɟɧɫɚɰɢɹ Ɇɢɯɚɷɥɹ 3-ɚɪɢɥɦɟɬɢɥɢɞɟɧ-3ɇ-ɮɭɪɚɧ-2-ɨɧɨɜ (1a,b) ɫ ɰɢɤɥɨɝɟɤɫɚ ɧɨɧɨɦ ɩɪɨɜɨɞɢɥɚɫɶ ɩɪɢ ɬɟɦɩɟɪɚɬɭɪɟ 60-65ɨɋ ɜ ɭɫɥɨɜɢɹɯ ɨɫɧɨɜɧɨɝɨ ɤɚɬɚɥɢ ɡɚ (ɩɢɩɟɪɢɞɢɧ), ɪɚɫɬɜɨɪɢɬɟɥɶ-ɷɬɚɧɨɥ. Ʉɨɧɞɟɧɫɚɰɢɹ Ɇɢɯɚɷɥɹ ɜ ɪɹɞɭ 5-R-3-ɚɪɢɥɦɟɬɢɥɢɞɟɧ-3ɇ-ɮɭɪɚɧ-2-ɨɧɨɜ (1c-e) ɫ ɚɰ ɟɬɢɥɚɰɟɬɨɧɨɦ ɩɪɨɜɨɞɢɥɚɫɶ ɩɪɢ ɧɚɝɪɟɜɚɧɢɢ ɪɟɚɝɟɧɬɨɜ (60-65ɨɋ) ɜ ɪɚɫɬɨɪɟ ɷɬɚɧɨɥɚ ɜ ɭɫɥɨɜɢɹɯ ɨɫɧɨɜɧɨɝɨ ɤɚɬɚɥɢɡɚ. Ɉɞɧɢɦ ɢɡ ɜɨɡɦɨɠɧɵɯ ɤɥɚɫɫɨɜ ɞɥɹ ɩɨɥɭɱɟɧɢɹ ɩɢɪɢɞɢɧɨɜɵɯ ɫɢɫɬɟɦ ɹɜɢɥɢɢ ɫɶ ɞɨɫɬɚɬɨɱɧɨ ɞɨɫɬɭɩɧɵɟ 5-ɚɪɢɥ-3-ɚɪɢɥɦɟɬɢɥɢɞɟɧ-3ɇ-ɮɭɪɚɧ-2-ɨɧɵ.

The yield of the product is 50%, which is compared to that of the way the raw material was pure 2-methylnaphthalene. Ɋɹɞ ˈɚɜɬɨɪɨɜ ɩɪɟɞɥɚɝɚɸɬ ɢɫɩɨɥɶɡɨɜɚɬɶ ɜ ɤɚɱɟɫɬɜɟ ɫɵɪɶɹ 2-ɦɟɬɢɥ-1- ɧɚɮɬ ɨɥ ɝɞɟ ɟɝɨ ɨɤˈɢɫɥɟɧɢɟ ɞɨ 2-ɦɟɬɢɥ-1,4-ɧɚɮɬɨɯɢɧɨɧɚ ɩɪɨɢɫɯɨɞɢɬ ɜ ɩɪɢ- ɫɭɬɫ ɬ ɜɢɢ ɤɚɬɚɥɢɡɚɬɨɪɨɜ [1,2] ɢɥɢ ɛɟɡ ɧɢɯ [3]. The dependence of regioselectivity and diastereoselectivity of 1,3-dipolar cycloaddition of nitrile oxides to Į,ȕ-unsaturated esters from the range of Į-D-xylo-pentadialdo-1,4-furanoze and Į-D-galacto-gexadialdo-1, 4-pyranoze has been investigated based on double bond geometry and nitrile oxide generation method.

These catalysts have high activity, selectivity up to 98%, and stability that offer real prospects for practical realization of the process.

Ɉɩɢɫɚɧɢɟ ɛɢɨɥɨɝɢɱɟɫɤɨɣ ɚɤɬɢɜɧɨɫɬɢ

Ⱦɥɹ ɢɫɤɥɸɱɟɧɢɹ ɫɥɟɩɨɝɨ ɩɨɢɫɤɚ ɛɢɨɥɨɝɢɟɫɤɨɣ ɚɤɬɢɜɧɧɭɭ ɪɨɜɚɧɧɢɣ ɧɚɦɢ ɩɪɨɜɟɞɟɧɨ ɦɚɬɟɦɚɬɢɱɟɫɨɢɞɞ ɭɥ (Vɚ-h). 4-Benzoyl-5-phenyl-2,3-di(phenylimino)-2,3-dihydrofuran was obtained by reactions of dibenzoylmethane with N-[1,2-dichloro-2-(phenylimino)ethylidene]benzeneamine. ɂ ɨɦɭ, ɧɟ ɢɡɦɟɧɹɟɬ ɧɚɩɪɚɜɥɟɧɢɟ ɪɟɚɤɰɢɢ ɚɡɚ-ȼɢɬɬɢɝɚɪɬɭɭɭɬɭɬ

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