ɀ ɍ Ɋ ɇ Ⱥ Ʌ ɋ Ɍ Ɋ ɍ Ʉ... Ɍɨɦ 47, ʋ 4 ɂɸɥɶ – ɚɜɝɭɫɬ ɋ. 648 – 653
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ɀɍɊɇȺɅ ɋɌɊɍɄɌɍɊɇɈɃ ɏɂɆɂɂ 2006. Ɍɨɦ 47, ʋ 4 ɂɸɥɶ – ɚɜɝɭɫɬ ɋ. 648 – 653 ɍȾɄ 539.194.01 ɋɉȿɄɌɊɈɋɄɈɉɂɑȿɋɄɈȿ ȼɕɑɂɋɅȿɇɂȿ ɗɇȿɊȽɂɃ ȾɂɋɋɈɐɂȺɐɂɂ ɋȼəɁȿɃ CH ȺɅɂɎȺɌɂɑȿɋɄɂɏ ɉɊɈɂɁȼɈȾɇɕɏ ɊəȾȺ ɗɌɂɅȿɇȺ 2006 Ʌ.Ⱥ. Ƚɪɢɛɨɜ1, ɂ.Ⱥ. ɇɨɜɚɤɨɜ2, Ⱥ.ɂ. ɉɚɜɥɸɱɤɨ2*, ɂ.ȼ. Ʉɭɱɭɪɨɜ2 1 ɂɧɫɬɢɬɭɬ ɝɟɨɯɢɦɢɢ ɢ ɚɧɚɥɢɬɢɱɟɫɤɨɣ ɯɢɦɢɢ ɢɦ ȼ.ɂ. ȼɟɪɧɚɞɫɤɨɝɨ, Ɇɨɫɤɜɚ ȼɨɥɝɨɝɪɚɞɫɤɢɣ ɝɨɫɭɞɚɪɫɬɜɟɧɧɵɣ ɬɟɯɧɢɱɟɫɤɢɣ ɭɧɢɜɟɪɫɢɬɟɬ 2 ɋɬɚɬɶɹ ɩɨɫɬɭɩɢɥɚ 5 ɞɟɤɚɛɪɹ 2005 ɝ. ɋ ɩɨɦɨɳɶɸ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɨɝɨ ɦɟɬɨɞɨɜ ɨɩɪɟɞɟɥɟɧɚ ɷɧɟɪɝɢɹ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɋɇ ɜ ɦɨɥɟɤɭɥɚɯ ɝɨɦɨɥɨɝɢɱɟɫɤɨɝɨ ɪɹɞɚ ɷɬɢɥɟɧɚ. ɋɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɟ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɪɚɫɫɱɢɬɵɜɚɥɢ ɧɚ ɨɫɧɨɜɟ ɮɭɧɞɚɦɟɧɬɚɥɶɧɵɯ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ ɜ ɚɧɝɚɪɦɨɧɢɱɟɫɤɨɦ ɩɪɢɛɥɢɠɟɧɢɢ ɜɚɪɢɚɰɢɨɧɧɵɦ ɦɟɬɨɞɨɦ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ Ɇɨɪɡɟɜɫɤɨ-ɚɧɝɚɪɦɨɧɢɱɟɫɤɨɝɨ ɛɚɡɢɫɚ. Ʉɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɢɟ ɜɵɱɢɫɥɟɧɢɹ ɩɪɨɢɡɜɨɞɢɥɢ ɫ ɢɫɩɨɥɶɡɨɜɚɧɢɟɦ ɛɚɡɢɫɚ 6-311G(3d, 3p)/B3LYP. ɉɪɨɜɟɞɟɧɨ ɨɛɫɭɠɞɟɧɢɟ ɩɨɥɭɱɟɧɧɵɯ ɡɚɤɨɧɨɦɟɪɧɨɫɬɟɣ ɢɡɦɟɧɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɩɪɢ ɢɡɦɟɧɟɧɢɢ ɫɬɪɭɤɬɭɪɵ ɦɨɥɟɤɭɥɵ. Ʉ ɥ ɸ ɱ ɟ ɜ ɵ ɟ ɫ ɥ ɨ ɜ ɚ : ɚɧɝɚɪɦɨɧɢɱɟɫɤɢɣ ɪɚɫɱɟɬ, ɷɧɟɪɝɢɹ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ, ɚɥɢɮɚɬɢɱɟɫɤɢɟ ɩɪɨɢɡɜɨɞɧɵɟ ɪɹɞɚ ɷɬɢɥɟɧɚ. ȼȼȿȾȿɇɂȿ ɗɧɟɪɝɢɹ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɹɜɥɹɟɬɫɹ ɨɞɧɨɣ ɢɡ ɜɚɠɧɟɣɲɢɯ ɜɟɥɢɱɢɧ, ɯɚɪɚɤɬɟɪɢɡɭɸɳɢɯ ɬɟɪɦɨɞɢɧɚɦɢɱɟɫɤɢɟ ɢ ɪɟɚɤɰɢɨɧɧɵɟ ɫɜɨɣɫɬɜɚ ɦɨɥɟɤɭɥɵ. ɂɦɟɧɧɨ ɩɨɷɬɨɦɭ ɜ ɬɟɱɟɧɢɟ ɩɨɫɥɟɞɧɢɯ ɫɬɚ ɥɟɬ ɜɵɩɨɥɧɟɧɨ ɡɧɚɱɢɬɟɥɶɧɨɟ ɤɨɥɢɱɟɫɬɜɨ ɪɚɛɨɬ, ɩɨɫɜɹɳɟɧɧɵɯ ɨɩɪɟɞɟɥɟɧɢɸ ɷɬɨɣ ɜɟɥɢɱɢɧɵ. ɉɪɢ ɷɬɨɦ ɫ ɬɟɱɟɧɢɟɦ ɜɪɟɦɟɧɢ ɤɨɥɢɱɟɫɬɜɨ ɬɚɤɢɯ ɪɚɛɨɬ ɩɨɫɬɨɹɧɧɨ ɭɜɟɥɢɱɢɜɚɟɬɫɹ, ɪɚɡɪɚɛɚɬɵɜɚɸɬɫɹ ɧɨɜɵɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɢ ɪɚɫɱɟɬɧɵɟ ɦɟɬɨɞɵ ɨɩɪɟɞɟɥɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ. ɋɥɟɞɭɟɬ ɢɦɟɬɶ ɜɜɢɞɭ, ɱɬɨ ɩɪɢ ɜɫɟɣ ɜɚɠɧɨɫɬɢ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɨɧɚ ɨɬɧɨɫɢɬɫɹ ɤ ɤɥɚɫɫɭ ɬɚɤ ɧɚɡɵɜɚɟɦɵɯ ɧɟɱɟɬɤɨ ɨɩɪɟɞɟɥɟɧɧɵɯ ɜɟɥɢɱɢɧ: ɨɧɚ ɪɚɜɧɚ ɪɚɡɧɨɫɬɢ ɫɭɦɦɵ ɷɧɟɪɝɢɢ ɪɚɞɢɤɚɥɨɜ ɢ ɢɫɯɨɞɧɨɣ ɦɨɥɟɤɭɥɵ, ɚ ɡɧɚɱɢɬ, ɫɢɥɶɧɨ ɡɚɜɢɫɢɬ ɨɬ ɬɨɝɨ, ɜ ɤɚɤɨɦ ɷɧɟɪɝɟɬɢɱɟɫɤɨɦ ɫɨɫɬɨɹɧɢɢ ɧɚɯɨɞɢɬɫɹ ɢɫɯɨɞɧɚɹ ɦɨɥɟɤɭɥɚ ɢ ɜ ɤɚɤɢɯ ɷɧɟɪɝɟɬɢɱɟɫɤɢɯ ɫɨɫɬɨɹɧɢɹɯ ɨɤɚɡɵɜɚɸɬɫɹ ɩɨɥɭɱɟɧɧɵɟ ɪɚɞɢɤɚɥɵ. ɗɬɨ ɩɪɢɜɨɞɢɬ ɤ ɬɨɦɭ, ɱɬɨ ɪɚɡɥɢɱɧɵɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɦɟɬɨɞɵ ɞɚɸɬ ɫɭɳɟɫɬɜɟɧɧɨ ɪɚɡɥɢɱɧɵɟ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ [ 1, 2 ]. Ɉɬɥɢɱɢɹ ɡɧɚɱɟɧɢɣ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ, ɧɚɣɞɟɧɧɵɯ ɪɚɡɥɢɱɧɵɦɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦɢ ɦɟɬɨɞɚɦɢ, ɞɨɫɬɢɝɚɸɬ 20 %. ɉɪɢ ɜɵɱɢɫɥɟɧɢɢ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɪɚɡɥɢɱɧɵɦɢ ɬɟɨɪɟɬɢɱɟɫɤɢɦɢ ɦɟɬɨɞɚɦɢ ɚɜɬɨɪɵ ɬɚɤɠɟ ɡɚɤɥɚɞɵɜɚɸɬ ɪɚɡɥɢɱɧɵɟ ɩɪɟɞɩɨɥɨɠɟɧɢɹ ɨɛ ɷɧɟɪɝɟɬɢɱɟɫɤɨɦ ɫɨɫɬɨɹɧɢɢ ɢɫɯɨɞɧɨɣ ɦɨɥɟɤɭɥɵ ɢ ɩɨɥɭɱɚɟɦɵɯ ɪɚɞɢɤɚɥɨɜ. ɇɚɩɪɢɦɟɪ, ɩɪɨɢɡɜɨɞɢɬɫɹ ɢɥɢ ɧɟ ɩɪɨɢɡɜɨɞɢɬɫɹ ɨɩɬɢɦɢɡɚɰɢɹ ɝɟɨɦɟɬɪɢɢ ɩɨɥɭɱɚɟɦɵɯ ɪɚɞɢɤɚɥɨɜ, ɭɱɢɬɵɜɚɟɬɫɹ ɢɥɢ ɧɟɬ ɬɟɦɩɟɪɚɬɭɪɧɚɹ ɡɚɫɟɥɟɧɧɨɫɬɶ ɤɨɥɟɛɚɬɟɥɶɧɵɯ ɢ ɜɪɚɳɚɬɟɥɶɧɵɯ ɭɪɨɜɧɟɣ ɷɧɟɪɝɢɢ ɢɫɯɨɞɧɨɣ ɦɨɥɟɤɭɥɵ ɢ ɩɨɥɭɱɚɟɦɵɯ ɪɚɞɢɤɚɥɨɜ ɢ ɬɚɤ ɞɚɥɟɟ. ȼ ɪɟɡɭɥɶɬɚɬɟ ɧɟɥɶɡɹ ɨɠɢɞɚɬɶ ɯɨɪɨɲɟɝɨ ɫɨɝɥɚɫɢɹ ɡɧɚɱɟɧɢɣ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɞɥɹ ɪɚɡɥɢɱɧɵɯ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɢ ɪɚɫɱɟɬɧɵɯ ɦɟɬɨɞɨɜ. ȼ ɥɭɱɲɟɦ ɫɥɭɱɚɟ ɦɨɠɧɨ ɧɚɞɟɹɬɶɫɹ ɥɢɲɶ ɧɚ ɫɨɝɥɚɫɢɟ ɬɟɧɞɟɧɰɢɢ ɢɡɦɟɧɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɨɩɪɟɞɟɥɟɧɧɨɣ ɫɜɹɡɢ ɜ ɪɹɞɭ ɦɨɥɟɤɭɥ. Ɉɞɧɢɦ ɢɡ ɜɨɡɦɨɠɧɵɯ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɢ ɪɚɫɱɟɬɧɵɯ ɦɟɬɨɞɨɜ ɨɩɪɟɞɟɥɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɹɜɥɹɟɬɫɹ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɣ ɦɟɬɨɞ. ɂɦɟɧɧɨ ɫ ɩɨɦɨɳɶɸ ɷɬɨɝɨ ɦɟɬɨɞɚ ɜ ɩɟɪ* E-mail: pavl@vstu.ru ɗɇȿɊȽɂɂ ȾɂɋɋɈɐɂȺɐɂɂ ɋȼəɁȿɃ ɋɇ ȺɅɂɎȺɌɂɑȿɋɄɂɏ ɉɊɈɂɁȼɈȾɇɕɏ ɊəȾȺ ɗɌɂɅȿɇȺ 649 ɜɨɣ ɩɨɥɨɜɢɧɟ XX ɜɟɤɚ ɛɵɥɚ ɨɩɪɟɞɟɥɟɧɚ ɷɧɟɪɝɢɹ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɞɜɭɯɚɬɨɦɧɵɯ ɦɨɥɟɤɭɥ [ 3 ]. ȼ ɩɨɫɥɟɞɧɢɟ ɝɨɞɵ ɜ ɫɜɹɡɢ ɫ ɩɪɨɝɪɟɫɫɨɦ ɜ ɥɚɡɟɪɧɨɣ ɫɩɟɤɬɪɨɫɤɨɩɢɢ ɪɚɡɜɢɜɚɟɬɫɹ ɚɧɚɥɨɝɢɱɧɵɣ ɦɟɬɨɞ ɞɥɹ ɦɧɨɝɨɚɬɨɦɧɵɯ ɦɨɥɟɤɭɥ [ 4 — 6 ]. Ɍɪɚɞɢɰɢɨɧɧɚɹ ɂɄ ɫɩɟɤɬɪɨɫɤɨɩɢɹ ɜ ɨɛɥɚɫɬɢ 600—4000 ɫɦ–1 ɬɚɤɠɟ ɦɨɠɟɬ ɞɚɬɶ ɝɪɨɦɚɞɧɵɣ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɦɚɬɟɪɢɚɥ ɞɥɹ ɨɩɪɟɞɟɥɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ XH, ɬɚɤ ɤɚɤ ɫ ɧɢɦɢ ɫɜɹɡɚɧɵ, ɯɨɬɹ ɢ ɞɨɫɬɚɬɨɱɧɨ ɫɥɨɠɧɵɦ ɨɛɪɚɡɨɦ, ɱɚɫɬɨɬɵ ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɮɭɧɞɚɦɟɧɬɚɥɶɧɵɯ ɤɨɥɟɛɚɧɢɣ. Ɉɞɧɢɦ ɢɡ ɪɚɡɜɢɜɚɸɳɢɯɫɹ ɩɨɞɯɨɞɨɜ ɹɜɥɹɟɬɫɹ ɢɫɩɨɥɶɡɨɜɚɧɢɟ ɷɦɩɢɪɢɱɟɫɤɢɯ ɤɨɪɪɟɥɹɰɢɣ [ 7 — 10 ] ɦɟɠɞɭ ɷɧɟɪɝɢɟɣ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɢ ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɦɢ ɢɦ ɱɚɫɬɨɬɚɦɢ ɮɭɧɞɚɦɟɧɬɚɥɶɧɵɯ ɤɨɥɟɛɚɧɢɣ ɦɨɥɟɤɭɥ ɢ ɪɚɞɢɤɚɥɨɜ. ɆȿɌɈȾɕ ȼɕɑɂɋɅȿɇɂə ɗɇȿɊȽɂɂ ȾɂɋɋɈɐɂȺɐɂɂ ɋȼəɁȿɃ ȼ ɪɚɡɜɢɜɚɟɦɨɦ ɧɚɦɢ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɦ ɦɟɬɨɞɟ ɷɧɟɪɝɢɹ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɨɩɪɟɞɟɥɹɟɬɫɹ ɪɚɫɱɟɬɧɵɦ ɩɭɬɟɦ ɧɚ ɨɫɧɨɜɟ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɫɩɟɤɬɪɨɜ ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɨɛɥɚɫɬɢ [ 11 — 15 ]. ɂɞɟɣɧɨ ɷɬɨɬ ɦɟɬɨɞ ɩɨɞɨɛɟɧ ɨɩɪɟɞɟɥɟɧɢɸ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɞɜɭɯɚɬɨɦɧɨɣ ɦɨɥɟɤɭɥɵ ɩɨ ɟɟ ɤɨɥɟɛɚɬɟɥɶɧɨɦɭ ɫɩɟɤɬɪɭ [ 3 ]. Ɉɬɥɢɱɢɟ ɫɨɫɬɨɢɬ ɜ ɬɨɦ, ɱɬɨ ɜ ɧɚɲɟɦ ɫɥɭɱɚɟ ɩɪɢɦɟɧɹɟɬɫɹ ɜɚɪɢɚɰɢɨɧɧɵɣ ɚɧɝɚɪɦɨɧɢɱɟɫɤɢɣ ɪɚɫɱɟɬ ɤɨɥɟɛɚɬɟɥɶɧɨɝɨ ɫɩɟɤɬɪɚ ɦɧɨɝɨɚɬɨɦɧɨɣ ɦɨɥɟɤɭɥɵ ɜ ɫɦɟɲɚɧɧɨɦ Ɇɨɪɡɟɜɫɤɨ-ɝɚɪɦɨɧɢɱɟɫɤɨɦ ɛɚɡɢɫɟ [ 11 ]. ɉɨɬɟɧɰɢɚɥɶɧɭɸ ɮɭɧɤɰɢɸ ɦɨɥɟɤɭɥɵ ɡɚɩɢɫɵɜɚɟɦ ɜ ɜɢɞɟ ɫɭɦɦɵ ɚɧɝɚɪɦɨɧɢɱɟɫɤɢɯ ɮɭɧɤɰɢɣ Ɇɨɪɡɟ ɞɥɹ ɤɨɨɪɞɢɧɚɬ ɪɚɫɬɹɠɟɧɢɹ ɫɜɹɡɟɣ X—H ɢ ɝɚɪɦɨɧɢɱɟɫɤɢɯ ɩɚɪɚɛɨɥ ɞɥɹ ɜɫɟɯ ɨɫɬɚɥɶɧɵɯ ɤɨɥɟɛɚɬɟɥɶɧɵɯ ɤɨɨɪɞɢɧɚɬ. Ɋɚɜɧɨɜɟɫɧɭɸ ɝɟɨɦɟɬɪɢɸ ɦɨɥɟɤɭɥ, ɧɚɱɚɥɶɧɨɟ ɩɪɢɛɥɢɠɟɧɢɟ ɩɨɬɟɧɰɢɚɥɶɧɨɣ ɮɭɧɤɰɢɢ ɢ ɢɡɦɟɧɟɧɢɹ ɞɢɩɨɥɶɧɨɝɨ ɦɨɦɟɧɬɚ ɦɨɥɟɤɭɥɵ ɩɪɢ ɟɟ ɤɨɥɟɛɚɧɢɹɯ ɧɚɯɨɞɢɥɢ ɫ ɩɨɦɨɳɶɸ ab initio ɜɵɱɢɫɥɟɧɢɣ ɜ ɛɚɡɢɫɟ 6-311G(3df, 3pd)/B3LYP. ɉɚɪɚɦɟɬɪɵ ɩɨɬɟɧɰɢɚɥɶɧɨɣ ɮɭɧɤɰɢɢ ɭɬɨɱɧɹɥɢ ɫ ɩɨɦɨɳɶɸ ɦɚɫɲɬɚɛɢɪɭɸɳɢɯ ɦɧɨɠɢɬɟɥɟɣ. ɗɧɟɪɝɢɸ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɩɨɞɛɢɪɚɥɢ ɢɧɞɢɜɢɞɭɚɥɶɧɨ ɞɨ ɫɨɜɩɚɞɟɧɢɹ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɢ ɜɵɱɢɫɥɟɧɧɵɯ ɜ ɚɧɝɚɪɦɨɧɢɱɟɫɤɨɦ ɩɪɢɛɥɢɠɟɧɢɢ ɮɭɧɞɚɦɟɧɬɚɥɶɧɵɯ ɩɨɥɨɫ ɩɨɝɥɨɳɟɧɢɹ, ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɜɚɥɟɧɬɧɵɦ ɤɨɥɟɛɚɧɢɹɦ ɷɬɢɯ ɫɜɹɡɟɣ. Ɋɟɲɟɧɢɟ ɡɚɞɚɱɢ ɞɨɜɨɞɢɥɢ ɞɨ ɩɨɫɬɪɨɟɧɢɹ ɤɪɢɜɨɣ ɩɨɝɥɨɳɟɧɢɹ ɜ ɂɄ ɫɩɟɤɬɪɟ. ɉɨɥɭɱɟɧɧɵɟ ɜ ɢɬɨɝɟ ɩɨɬɟɧɰɢɚɥɶɧɵɟ ɢ ɷɥɟɤɬɪɨɨɩɬɢɱɟɫɤɢɟ ɮɭɧɤɰɢɢ ɯɨɪɨɲɨ ɜɨɫɩɪɨɢɡɜɨɞɹɬ ɂɄ ɫɩɟɤɬɪɵ ɪɚɫɫɦɚɬɪɢɜɚɟɦɵɯ ɦɨɥɟɤɭɥ. Ɉɧɢ ɦɨɝɭɬ ɛɵɬɶ ɩɨɥɭɱɟɧɵ ɭ ɚɜɬɨɪɨɜ. ɇɟɨɛɯɨɞɢɦɨ ɭɱɢɬɵɜɚɬɶ, ɱɬɨ ɜ ɧɚɲɟɦ ɦɟɬɨɞɟ ɩɪɟɞɩɨɥɚɝɚɟɬɫɹ ɧɟɢɡɦɟɧɧɨɟ ɝɟɨɦɟɬɪɢɱɟɫɤɨɟ ɫɬɪɨɟɧɢɟ ɪɚɞɢɤɚɥɚ ɩɪɢ ɪɚɡɪɵɜɟ ɫɜɹɡɢ ɜ ɦɨɥɟɤɭɥɟ. ɗɬɨ ɫɜɹɡɚɧɨ ɫɨ ɫɦɵɫɥɨɦ ɩɨɬɟɧɰɢɚɥɶɧɨɣ ɮɭɧɤɰɢɢ ɜ ɤɨɥɟɛɚɬɟɥɶɧɨɦ ɪɚɫɱɟɬɟ. ɉɨɥɭɱɟɧɧɵɟ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɡɚɜɵɲɟɧɵ ɢɡ-ɡɚ ɨɫɨɛɟɧɧɨɫɬɟɣ ɮɭɧɤɰɢɢ Ɇɨɪɡɟ [ 3, 11 ]. ɉɨɷɬɨɦɭ ɜɫɟ ɪɚɫɫɱɢɬɚɧɧɵɟ ɜɟɥɢɱɢɧɵ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɛɵɥɢ ɭɦɟɧɶɲɟɧɵ ɧɚ ɜɟɥɢɱɢɧɭ, ɪɚɜɧɭɸ 90 ɤȾɠ/ɦɨɥɶ. ȼ ɧɚɲɟɦ ɦɟɬɨɞɟ ɩɪɢ ɜɵɱɢɫɥɟɧɢɢ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɧɟ ɜɨɡɧɢɤɚɟɬ ɩɪɨɛɥɟɦɵ ɭɱɟɬɚ ɬɟɦɩɟɪɚɬɭɪɧɨɣ ɡɚɫɟɥɟɧɧɨɫɬɢ ɤɨɥɟɛɚɬɟɥɶɧɵɯ ɭɪɨɜɧɟɣ ɷɧɟɪɝɢɢ, ɬɚɤ ɤɚɤ ɢɯ ɜɵɱɢɫɥɹɸɬ ɧɚ ɨɫɧɨɜɚɧɢɢ ɱɚɫɬɨɬ ɤɨɥɟɛɚɧɢɣ, ɫɨɨɬɜɟɬɫɬɜɭɸɳɢɯ ɤɨɦɧɚɬɧɨɣ ɬɟɦɩɟɪɚɬɭɪɟ. ɇɚɦɢ ɩɪɨɢɡɜɨɞɢɥɨɫɶ ɬɚɤɠɟ ɜɵɱɢɫɥɟɧɢɟ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɋɇ ɫ ɩɨɦɨɳɶɸ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɨɝɨ ɦɟɬɨɞɚ. ɗɬɨ ɩɨɡɜɨɥɢɥɨ ɫɨɨɬɧɟɫɬɢ ɜɵɱɢɫɥɟɧɧɵɟ ɬɚɤɢɦ ɦɟɬɨɞɨɦ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɫɨ ɡɧɚɱɟɧɢɹɦɢ, ɩɨɥɭɱɟɧɧɵɦɢ ɫ ɩɨɦɨɳɶɸ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɦɟɬɨɞɚ, ɚ ɬɚɤɠɟ ɩɪɨɚɧɚɥɢɡɢɪɨɜɚɬɶ ɜɨɡɦɨɠɧɵɟ ɨɲɢɛɤɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɪɟɡɭɥɶɬɚɬɨɜ. ɗɧɟɪɝɢɸ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɜ ɞɚɧɧɨɦ ɦɟɬɨɞɟ ɦɵ ɨɩɪɟɞɟɥɹɥɢ ɤɚɤ ɪɚɡɧɢɰɭ ɷɧɟɪɝɢɢ ɦɨɥɟɤɭɥɵ ɫ ɫɭɦɦɨɣ ɷɧɟɪɝɢɣ ɫɜɨɛɨɞɧɨɝɨ ɪɚɞɢɤɚɥɚ ɢ ɚɬɨɦɚ ɜɨɞɨɪɨɞɚ. ɗɬɢ ɷɧɟɪɝɢɢ ɜɵɱɢɫɥɹɥɢ ɫ ɩɨɦɨɳɶɸ ɩɪɨɝɪɚɦɦɵ GAMESS [ 16 ] ɜ ɛɚɡɢɫɟ 6-311G(3df, 3pd)/B3LYP. ȼ ɪɚɫɱɟɬɚɯ ɢɫɩɨɥɶɡɨɜɚɥɢ ɝɟɨɦɟɬɪɢɸ ɦɨɥɟɤɭɥɵ, ɨɩɬɢɦɢɡɢɪɨɜɚɧɧɭɸ ɜ ɷɬɨɦ ɠɟ ɛɚɡɢɫɟ. Ƚɟɨɦɟɬɪɢɹ ɪɚɞɢɤɚɥɚ ɩɨɥɧɨɫɬɶɸ ɫɨɜɩɚɞɚɥɚ (ɡɚ ɢɫɤɥɸɱɟɧɢɟɦ ɨɬɪɵɜɚɟɦɨɝɨ ɚɬɨɦɚ ɇ) ɫ ɝɟɨɦɟɬɪɢɟɣ ɦɨɥɟɤɭɥɵ. Ɉɩɬɢɦɢɡɚɰɢɹ ɝɟɨɦɟɬɪɢɢ ɪɚɞɢɤɚɥɚ ɜɪɹɞ ɥɢ ɦɨɠɟɬ ɩɨɜɵɫɢɬɶ ɬɨɱɧɨɫɬɶ ɜɵɱɢɫɥɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ, ɬɚɤ ɤɚɤ ɪɚɞɢɤɚɥɵ ɪɚɫɫɱɢɬɵɜɚɸɬ ɫ ɝɨɪɚɡɞɨ ɦɟɧɶɲɟɣ ɬɨɱɧɨɫɬɶɸ, ɱɟɦ ɫɜɨɛɨɞɧɵɟ ɦɨɥɟɤɭɥɵ. ȿɳɟ ɫ ɦɟɧɶɲɟɣ ɬɨɱɧɨɫɬɶɸ ɜɨɡɦɨɠɟɧ ɪɚɫɱɟɬ ɱɚɫɬɨɬ ɤɨɥɟɛɚɧɢɣ ɪɚɞɢɤɚɥɨɜ. ɉɨ ɷɬɨɣ ɩɪɢɱɢɧɟ ɩɪɢ ɜɵɱɢɫɥɟɧɢɹɯ ɦɵ ɧɟ ɭɱɢɬɵɜɚɥɢ ɡɚɫɟɥɟɧɧɨɫɬɶ ɤɨɥɟɛɚɬɟɥɶɧɵɯ ɭɪɨɜɧɟɣ ɷɧɟɪɝɢɢ, ɢ ɜɵɱɢɫɥɟɧɧɚɹ ɜɟɥɢɱɢɧɚ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɫɨɨɬɜɟɬɫɬɜɨɜɚɥɚ ɚɛɫɨɥɸɬɧɨɦɭ ɧɭɥɸ ɬɟɦɩɟɪɚɬɭɪɵ. 650 Ʌ.Ⱥ. ȽɊɂȻɈȼ, ɂ.Ⱥ. ɇɈȼȺɄɈȼ, Ⱥ.ɂ. ɉȺȼɅɘɑɄɈ, ɂ.ȼ. ɄɍɑɍɊɈȼ ȺɇȺɅɂɁ ȼɕɑɂɋɅȿɇɇɕɏ ɁɇȺɑȿɇɂɃ ɗɇȿɊȽɂɂ ȾɂɋɋɈɐɂȺɐɂɂ ɋȼəɁȿɃ ɉɪɨɜɟɞɟɧɵ ɜɵɱɢɫɥɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɚɥɢɮɚɬɢɱɟɫɤɢɯ ɩɪɨɢɡɜɨɞɧɵɯ ɪɹɞɚ ɷɬɢɥɟɧɚ: ɷɬɟɧɚ, 1-ɩɪɨɩɟɧɚ, 2-ɦɟɬɢɥ-1-ɩɪɨɩɟɧɚ, 1-ɛɭɬɟɧɚ, ɬɪɚɧɫ-2-ɛɭɬɟɧɚ, ɰɢɫ-2-ɛɭɬɟɧɚ, 2-ɦɟɬɢɥ2-ɛɭɬɟɧɚ, 2,3-ɞɢɦɟɬɢɥ-2-ɛɭɬɟɧɚ, 1,3-ɛɭɬɚɞɢɟɧɚ ɢ 2-ɦɟɬɢɥ-1,3-ɛɭɬɚɞɢɟɧɚ. Ⱦɥɹ ɞɚɧɧɵɯ ɫɨɟɞɢɧɟɧɢɣ ɜ ɷɤɫɩɟɪɢɦɟɧɬɟ ɪɚɡɪɟɲɟɧɵ ɩɨɥɨɫɵ ɩɨɝɥɨɳɟɧɢɹ ɞɥɹ ɜɫɟɯ ɫɜɹɡɟɣ CH. ɗɬɨ ɩɨɡɜɨɥɢɥɨ ɧɚɦ ɩɪɨɢɡɜɟɫɬɢ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɣ ɪɚɫɱɟɬ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɞɥɹ ɤɚɠɞɨɣ ɫɜɹɡɢ CH. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɢ ɪɚɫɫɱɢɬɚɧɧɵɟ ɫɩɟɤɬɪɵ ɩɨɝɥɨɳɟɧɢɹ ɩɪɢɜɟɞɟɧɵ ɧɚ ɪɢɫ. 1— 10. Ɋɟɡɭɥɶɬɚɬɵ ɜɵɱɢɫɥɟɧɢɣ ɩɪɢɜɟɞɟɧɵ ɜ ɬɚɛɥɢɰɟ. Ⱦɥɹ ɫɪɚɜɧɟɧɢɹ ɬɚɦ ɠɟ ɩɪɢɜɟɞɟɧɵ ɡɧɚɱɟɧɢɹ ɞɥɹ ɦɨɥɟɤɭɥɵ ɩɪɨɩɚɧɚ. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɜɡɹɬɵ ɢɡ ɪɚɛɨɬ [ 1, 2 ]. ɉɪɢ ɫɨɩɨɫɬɚɜɥɟɧɢɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɢɯ ɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɯ ɷɧɟɪɝɢɣ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɧɟɨɛɯɨɞɢɦɨ ɭɱɢɬɵɜɚɬɶ, ɱɬɨ ɪɚɫɱɟɬɧɚɹ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɚɹ ɜɟɥɢɱɢɧɚ ɡɚɜɵɲɟɧɚ ɜ ɫɪɟɞɧɟɦ ɧɚ 65 ɤȾɠ/ɦɨɥɶ ɢɡ-ɡɚ ɨɝɪɚɧɢɱɟɧɧɨɫɬɢ ɧɚɛɨɪɚ ɷɥɟɤɬɪɨɧɧɵɯ ɜɨɥɧɨɜɵɯ ɮɭɧɤɰɢɣ. ɉɪɢ ɚɧɚɥɢɡɟ ɩɨɥɭɱɟɧɧɵɯ ɪɟɡɭɥɶɬɚɬɨɜ ɩɪɟɠɞɟ ɜɫɟɝɨ ɨɛɪɚɳɚɟɬ ɧɚ ɫɟɛɹ ɜɧɢɦɚɧɢɟ ɬɨ, ɱɬɨ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɟ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɜ ɝɪɭɩɩɟ C=CH2 ɜ ɫɪɟɞɧɟɦ ɧɚ 50 ɤȾɠ/ɦɨɥɶ ɜɵɲɟ, ɱɟɦ ɞɥɹ ɫɜɹɡɟɣ CH ɜ ɝɪɭɩɩɟ ɋ—CH2—C ɜ ɦɨɥɟɤɭɥɟ ɩɪɨɩɚɧɚ. ɗɬɨɬ ɪɟɡɭɥɶɬɚɬ ɩɨɥɧɨɫɬɶɸ ɩɨɞɬɜɟɪɠɞɚɟɬɫɹ ɞɚɧɧɵɦɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɢɯ ɜɵɱɢɫɥɟɧɢɣ ɢ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɦɢ ɡɧɚɱɟɧɢɹɦɢ. Ɋɢɫ. 1. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ ɷɬɟɧɚ Ɋɢɫ. 2. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ 1-ɩɪɨɩɟɧɚ Ɋɢɫ. 3. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ 2-ɦɟɬɢɥ-1-ɩɪɨɩɟɧɚ Ɋɢɫ. 4. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ 1-ɛɭɬɟɧɚ ɗɇȿɊȽɂɂ ȾɂɋɋɈɐɂȺɐɂɂ ɋȼəɁȿɃ ɋɇ ȺɅɂɎȺɌɂɑȿɋɄɂɏ ɉɊɈɂɁȼɈȾɇɕɏ ɊəȾȺ ɗɌɂɅȿɇȺ 651 Ɋɢɫ. 5. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ ɬɪɚɧɫ-2-ɛɭɬɟɧɚ Ɋɢɫ. 6. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ ɰɢɫ-2-ɛɭɬɟɧɚ Ɋɢɫ. 7. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ 2-ɦɟɬɢɥ-2-ɛɭɬɟɧɚ Ɋɢɫ. 8. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ 2,3-ɞɢɦɟɬɢɥ-2-ɛɭɬɟɧɚ Ɋɢɫ. 9. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ 1,3-ɛɭɬɚɞɢɟɧɚ Ɋɢɫ. 10. ɗɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɣ ɢ ɪɚɫɫɱɢɬɚɧɧɵɣ ɫɩɟɤɬɪɵ 2-ɦɟɬɢɥ-1,3-ɛɭɬɚɞɢɟɧɚ 652 Ʌ.Ⱥ. ȽɊɂȻɈȼ, ɂ.Ⱥ. ɇɈȼȺɄɈȼ, Ⱥ.ɂ. ɉȺȼɅɘɑɄɈ, ɂ.ȼ. ɄɍɑɍɊɈȼ ɗɧɟɪɝɢɹ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ ɋH (ɤȾɠ/ɦɨɥɶ) Ɇɨɥɟɤɭɥɚ ɗɬɟɧ 1-ɉɪɨɩɟɧ 2-Ɇɟɬɢɥ-1-ɩɪɨɩɟɧ DCH ɜ CH Ɋɚɫɱɟɬ ɗɤɫɩ. ɋɩɟɤɪ. Ʉɏ – – – 438,8 492,6 – – – DCH ɜ CH2 Ɋɚɫɱɟɬ ɗɤɫɩ. ɋɩɟɤɪ. Ʉɏ 446,3 507,1 444,1c 444,1t 508,4c 509,7t 441,3 509,9 507,0c 508,5t 448,5r 428,91 444,02 1-Ȼɭɬɟɧ 433,5 490,9 443,0c 443,0t 394,8r ɬɪɚɧɫ-2-Ȼɭɬɟɧ 433,5 493,9 – – – ɰɢɫ-2-Ȼɭɬɟɧ 438,0 491,1 – – – 2-Ɇɟɬɢɥ-2-ɛɭɬɟɧ 433,5 490,8 – – – – – – 439,5a 449,8b 443,3a 443,3b 443,3d 443,3f 510,8a 513,1b 512,3a 513,0b 506,4c 511,1d 395,8 486,1 2,3-Ⱦɢɦɟɬɢɥ-2-ɛɭɬɟɧ 1,3-Ȼɭɬɚɞɢɟɧ 2-Ɇɟɬɢɥ-1,3-ɛɭɬɚɞɢɟɧ ɉɪɨɩɚɧ – – – 435,5 497,7 366,12 435,9 493,9 – – – DCH ɜ CH3 Ɋɚɫɱɟɬ ɋɩɟɤɪ. Ʉɏ – – 418,1p 407,9 415,1p 405,5 491,8p 465,3 492,2p 467,2 413,8p 411,7 489,4p 486,5 419,4p 404,7 422,2p 404,4 D 425,0p 399,0 E 425,0p 399,0 J 419,4p 404,7 425,0p 399,0 490,9p 462,4 487,2p 462,1 491,5p 464,4 487,6p 464,4 485,9p 459,4 481,0p 456,8 – – 421,4p 399,3 489,2p 468,7 410,2p 411,8 486,9p 470,2 ɗɤɫɩ. – 360,6 [ 1 ] 327,6 [ 1 ] 322,2 [ 2 ] 339,3 [ 2 ] 334,7 [ 2 ] – 397,5 [ 1 ] 409,9 [ 2 ] ɉ ɪ ɢ ɦ ɟ ɱ ɚ ɧ ɢ ɟ. D, E, J — ɢɧɞɟɤɫɵ ɩɪɢ ɝɪɭɩɩɚɯ-ɡɚɦɟɫɬɢɬɟɥɹɯ. a, b, d, f — ɢɧɞɟɤɫɵ ɩɪɢ ɧɟɷɤɜɢɜɚɥɟɧɬɧɵɯ ɫɜɹɡɹɯ ɋɇ. t — ɫɜɹɡɶ ɋɇ ɜ ɬɪɚɧɫ-ɩɨɥɨɠɟɧɢɢ ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ ɝɪɭɩɩɟ-ɡɚɦɟɫɬɢɬɟɥɸ. c — ɫɜɹɡɶ ɋɇ ɜ ɰɢɫ-ɩɨɥɨɠɟɧɢɢ ɩɨ ɨɬɧɨɲɟɧɢɸ ɤ ɝɪɭɩɩɟ-ɡɚɦɟɫɬɢɬɟɥɸ. r — ɫɜɹɡɶ ɋɇ ɜ ɝɪɭɩɩɟ-ɡɚɦɟɫɬɢɬɟɥɟ. p — ɫɜɹɡɶ ɋɇ, ɧɚɯɨɞɹɳɚɹɫɹ ɜ ɩɥɨɫɤɨɫɬɢ ɫɢɦɦɟɬɪɢɢ ɦɨɥɟɤɭɥɵ. ɉɪɢ ɡɚɦɟɳɟɧɢɢ ɚɬɨɦɚ ɜɨɞɨɪɨɞɚ ɜ ɝɪɭɩɩɟ C=CH2 ɧɚ ɦɟɬɢɥɶɧɭɸ ɢɥɢ ɷɬɢɥɶɧɭɸ ɝɪɭɩɩɭ ɩɪɨɢɫɯɨɞɢɬ ɭɦɟɧɶɲɟɧɢɟ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɢ ɋɇ ɜ ɨɛɪɚɡɭɸɳɟɣɫɹ ɝɪɭɩɩɟ C=CHR. ȼɟɥɢɱɢɧɚ ɷɬɨɝɨ ɩɨɧɢɠɟɧɢɹ ɩɨ ɞɚɧɧɵɦ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ ɜɚɪɶɢɪɭɟɬɫɹ ɨɬ 8 ɞɨ 13 ɤȾɠ/ɦɨɥɶ ɢ ɡɚɜɢɫɢɬ ɨɬ ɩɪɢɪɨɞɵ ɡɚɦɟɫɬɢɬɟɥɹ. ɉɪɢɦɟɪɧɨ ɬɚɤɭɸ ɠɟ ɜɟɥɢɱɢɧɭ ɩɨɧɢɠɟɧɢɹ ɞɚɟɬ ɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɢɣ ɪɚɫɱɟɬ. ɉɪɢ ɷɬɨɦ ɢɦɟɟɬɫɹ ɤɨɪɪɟɥɹɰɢɹ ɦɟɠɞɭ ɜɟɥɢɱɢɧɨɣ ɩɨɧɢɠɟɧɢɹ, ɜɵɱɢɫɥɟɧɧɨɣ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢɦ ɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɢɦ ɫɩɨɫɨɛɨɦ, ɢ ɩɪɢɪɨɞɨɣ ɡɚɦɟɫɬɢɬɟɥɹ. ȿɞɢɧɫɬɜɟɧɧɚɹ ɢɡɜɟɫɬɧɚɹ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɚɹ ɜɟɥɢɱɢɧɚ ɞɥɹ ɫɜɹɡɢ ɋɇ ɜ ɝɪɭɩɩɟ C=CH—CH=C ɦɨɥɟɤɭɥɵ 1,3ɛɭɬɚɞɢɟɧɚ ɬɚɤɠɟ ɫɜɢɞɟɬɟɥɶɫɬɜɭɟɬ ɜ ɩɨɥɶɡɭ ɧɚɛɥɸɞɚɟɦɨɝɨ ɩɨɧɢɠɟɧɢɹ. Ɉɞɧɚɤɨ ɞɚɧɧɚɹ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɚɹ ɜɟɥɢɱɢɧɚ, ɫɤɨɪɟɟ ɜɫɟɝɨ, ɧɟɞɨɫɬɚɬɨɱɧɨ ɬɨɱɧɚ, ɬɚɤ ɤɚɤ ɟɟ ɡɧɚɱɟɧɢɟ ɨɤɚɡɵɜɚɟɬɫɹ ɧɚ- ɗɇȿɊȽɂɂ ȾɂɋɋɈɐɂȺɐɂɂ ɋȼəɁȿɃ ɋɇ ȺɅɂɎȺɌɂɑȿɋɄɂɏ ɉɊɈɂɁȼɈȾɇɕɏ ɊəȾȺ ɗɌɂɅȿɇȺ 653 ɦɧɨɝɨ ɧɢɠɟ, ɱɟɦ ɞɥɹ ɫɜɹɡɟɣ CH ɩɪɢ ɩɟɪɜɢɱɧɵɯ, ɜɬɨɪɢɱɧɵɯ ɢ ɬɪɟɬɢɱɧɵɯ ɚɬɨɦɚɯ ɭɝɥɟɪɨɞɚ ɜ ɧɚɫɵɳɟɧɧɵɯ ɭɝɥɟɜɨɞɨɪɨɞɚɯ. ɋɨɝɥɚɫɧɨ ɞɚɧɧɵɦ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ ɞɥɹ ɫɜɹɡɟɣ CH ɜ ɝɪɭɩɩɟ H2C=C(R1)R2 ɬɚɤɠɟ ɧɚɛɥɸɞɚɟɬɫɹ ɧɟɛɨɥɶɲɨɟ ɩɨɧɢɠɟɧɢɟ ɢɯ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɩɨ ɫɪɚɜɧɟɧɢɸ ɫ ɦɨɥɟɤɭɥɨɣ ɷɬɟɧɚ ɜ ɫɪɟɞɧɟɦ ɧɚ 3 ɤȾɠ/ɦɨɥɶ. Ʉɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɢɣ ɪɚɫɱɟɬ ɧɟ ɞɚɟɬ ɬɚɤɨɝɨ ɩɨɧɢɠɟɧɢɹ. ȼ ɫɜɨɸ ɨɱɟɪɟɞɶ ɤɪɚɬɧɚɹ ɫɜɹɡɶ ɭɝɥɟɪɨɞ—ɭɝɥɟɪɨɞ ɩɪɢɜɨɞɢɬ ɤ ɢɡɦɟɧɟɧɢɸ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɜ ɦɟɬɢɥɶɧɨɦ ɢ ɷɬɢɥɶɧɨɦ ɡɚɦɟɫɬɢɬɟɥɹɯ. ȼɟɥɢɱɢɧɚ ɷɬɨɝɨ ɢɡɦɟɧɟɧɢɹ ɡɚɜɢɫɢɬ ɨɬ ɩɨɥɨɠɟɧɢɹ ɫɜɹɡɢ CH ɜ ɡɚɦɟɫɬɢɬɟɥɟ ɨɬɧɨɫɢɬɟɥɶɧɨ ɦɨɥɟɤɭɥɵ. Ⱦɥɹ ɫɜɹɡɟɣ CH ɦɟɬɢɥɶɧɨɝɨ ɡɚɦɟɫɬɢɬɟɥɹ, ɥɟɠɚɳɢɯ ɜ ɩɥɨɫɤɨɫɬɢ C=CH2 ɝɪɭɩɩɵ, ɫɨɝɥɚɫɧɨ ɞɚɧɧɵɦ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɨɜ, ɩɪɨɢɫɯɨɞɢɬ ɭɜɟɥɢɱɟɧɢɟ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɨɬ 5 ɞɨ 15 ɤȾɠ/ɦɨɥɶ. Ⱦɥɹ ɫɜɹɡɟɣCH ɦɟɬɢɥɶɧɨɝɨ ɡɚɦɟɫɬɢɬɟɥɹ, ɥɟɠɚɳɢɯ ɜɧɟ ɩɥɨɫɤɨɫɬɢ C=CH2 ɝɪɭɩɩɵ, ɷɧɟɪɝɢɹ ɞɢɫɫɨɰɢɚɰɢɢ ɭɦɟɧɶɲɚɟɬɫɹ. ɋɨɝɥɚɫɧɨ ɞɚɧɧɵɦ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɨɜ ɜɟɥɢɱɢɧɚ ɷɬɨɝɨ ɩɨɧɢɠɟɧɢɹ ɜɚɪɶɢɪɭɟɬɫɹ ɨɬ 4 ɞɨ 13 ɤȾɠ/ɦɨɥɶ. ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɫɨɝɥɚɫɧɨ ɞɚɧɧɵɦ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ ɤɪɚɬɧɚɹ ɫɜɹɡɶ ɭɝɥɟɪɨɞ—ɭɝɥɟɪɨɞ ɧɟ ɩɪɢɜɨɞɢɬ ɤ ɢɡɦɟɧɟɧɢɸ ɫɭɦɦɵ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɜ ɦɟɬɢɥɶɧɨɦ ɡɚɦɟɫɬɢɬɟɥɟ. ɉɪɨɢɫɯɨɞɢɬ ɥɢɲɶ ɩɟɪɟɪɚɫɩɪɟɞɟɥɟɧɢɟ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɦɟɠɞɭ ɩɥɨɫɤɨɫɬɧɵɦɢ ɢ ɧɟɩɥɨɫɤɨɫɬɧɵɦɢ ɫɜɹɡɹɦɢ CH. ɋɨɝɥɚɫɧɨ ɞɚɧɧɵɦ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ ɩɪɨɢɫɯɨɞɢɬ ɧɟɛɨɥɶɲɨɟ ɭɦɟɧɶɲɟɧɢɟ ɫɭɦɦɵ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɷɬɢɯ ɫɜɹɡɟɣ. ɂɦɟɸɳɢɟɫɹ ɷɤɫɩɟɪɢɦɟɧɬɚɥɶɧɵɟ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɜ ɦɟɬɢɥɶɧɨɦ ɡɚɦɟɫɬɢɬɟɥɟ ɫɤɨɪɟɟ ɜɫɟɝɨ ɧɟɞɨɫɬɚɬɨɱɧɨ ɬɨɱɧɵ, ɬɚɤ ɤɚɤ ɨɬɥɢɱɚɸɬɫɹ ɧɚ ɨɱɟɧɶ ɛɨɥɶɲɭɸ ɜɟɥɢɱɢɧɭ, ɞɨ 70 ɤȾɠ/ɦɨɥɶ, ɨɬ ɡɧɚɱɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɷɬɢɯ ɠɟ ɫɜɹɡɟɣ ɜ ɦɨɥɟɤɭɥɟ ɩɪɨɩɚɧɚ. ɋɨɝɥɚɫɧɨ ɞɚɧɧɵɦ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɨɝɨ ɢ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɨɜ ɜɥɢɹɧɢɟ ɤɪɚɬɧɨɣ ɫɜɹɡɢ ɭɝɥɟɪɨɞ—ɭɝɥɟɪɨɞ ɧɚ ɷɧɟɪɝɢɸ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɜ ɷɬɢɥɶɧɨɦ ɡɚɦɟɫɬɢɬɟɥɟ ɝɨɪɚɡɞɨ ɫɥɚɛɟɟ, ɱɟɦ ɜ ɦɟɬɢɥɶɧɨɦ. ɗɬɨ, ɜɢɞɢɦɨ, ɫɜɹɡɚɧɨ ɫ ɬɟɦ, ɱɬɨ ɫɜɹɡɶ CH ɜ ɦɟɬɢɥɶɧɨɣ ɝɪɭɩɩɟ, ɥɟɠɚɳɚɹ ɜ ɩɥɨɫɤɨɫɬɢ ɝɪɭɩɩɵ C=CH2, ɡɧɚɱɢɬɟɥɶɧɨ ɭɞɚɥɟɧɚ ɨɬ ɤɪɚɬɧɨɣ ɫɜɹɡɢ ɭɝɥɟɪɨɞ—ɭɝɥɟɪɨɞ, ɚ ɢɡɦɟɧɟɧɢɟ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH, ɥɟɠɚɳɢɯ ɜɧɟ ɷɬɨɣ ɩɥɨɫɤɨɫɬɢ, ɦɟɧɶɲɟ ɩɨ ɫɜɨɟɣ ɜɟɥɢɱɢɧɟ. ɋɥɟɞɭɟɬ ɨɬɦɟɬɢɬɶ, ɱɬɨ ɩɨɥɭɱɟɧɧɵɟ ɫɩɟɤɬɪɨɫɤɨɩɢɱɟɫɤɢ ɢɡɦɟɧɟɧɢɹ ɷɧɟɪɝɢɢ ɞɢɫɫɨɰɢɚɰɢɢ ɫɜɹɡɟɣ CH ɜ ɪɹɞɭ ɢɡɭɱɟɧɧɵɯ ɧɚɦɢ ɦɨɥɟɤɭɥ ɥɭɱɲɟ ɫɨɝɥɚɫɭɸɬɫɹ ɫ ɢɧɬɭɢɬɢɜɧɵɦɢ ɩɪɟɞɫɬɚɜɥɟɧɢɹɦɢ ɨ ɯɚɪɚɤɬɟɪɟ ɜɥɢɹɧɢɹ ɧɚ ɢɯ ɜɟɥɢɱɢɧɭ ɫɬɪɭɤɬɭɪɵ ɦɨɥɟɤɭɥɵ, ɱɟɦ ɞɚɧɧɵɟ ɤɜɚɧɬɨɜɨɯɢɦɢɱɟɫɤɨɝɨ ɪɚɫɱɟɬɚ. Ɋɚɛɨɬɚ ɩɨɞɞɟɪɠɚɧɚ ɝɪɚɧɬɨɦ Ɋɨɫɫɢɣɫɤɨɝɨ ɮɨɧɞɚ ɮɭɧɞɚɦɟɧɬɚɥɶɧɵɯ ɢɫɫɥɟɞɨɜɚɧɢɣ ʋ 05-0332017. ɋɉɂɋɈɄ ɅɂɌȿɊȺɌɍɊɕ 1. ɗɧɟɪɝɢɢ ɪɚɡɪɵɜɚ ɯɢɦɢɱɟɫɤɢɯ ɫɜɹɡɟɣ. ɉɨɬɟɧɰɢɚɥɵ ɢɨɧɢɡɚɰɢɢ ɢ ɫɪɨɞɫɬɜɨ ɤ ɷɥɟɤɬɪɨɧɭ / ɉɨɞ ɪɟɞ. ȼ.ɇ. Ʉɨɧɞɪɚɬɶɟɜɚ – Ɇ.: ɇɚɭɤɚ, 1974. – 315 ɫ. 2. Ɍɚɯɢɫɬɨɜ ȼ.ȼ. Ɉɪɝɚɧɢɱɟɫɤɚɹ ɦɚɫɫ-ɫɩɟɤɬɪɨɦɟɬɪɢɹ. – Ʌ.: ɇɚɭɤɚ, 1990. – 326 ɫ. 3. ȿɥɶɹɲɟɜɢɱ Ɇ.Ⱥ. Ⱥɬɨɦɧɚɹ ɢ ɦɨɥɟɤɭɥɹɪɧɚɹ ɫɩɟɤɬɪɨɫɤɨɩɢɹ. – Ɇ.: ȽɂɎɆɅ, 1962. – 892 ɫ. 4. Brown S.S., Berghout H.L., Crim F.F. // J. Chem. Phys. – 1996. – 105. – P. 8103 – 8110. 5. Martin J.D.D., Hepburn J.W. // Ibid. – 1998. – 109. – P. 8139 – 8142. 6. Shiell R.C., Hu X.K., Hu Q.J., Hepburn J.W. // J. Phys. Chem. A. – 2000. – 104. – P. 4339 – 4342. 7. Ponomarev D., Takhistov V. // J. Mol. Struct. – 1997. – 435. – P. 256 – 274. 8. Orlov Y.D., Bouchoux G., Takhistov V. et al. // Ibid. – 2002. – 608. – P. 109 – 122. 9. Golovin A.V., Takhistov V.V. // Ibid. – 2004. – 701. – P. 57 – 91. 10. Golovin A.V., Takhistov V.V. // Ibid. – 2005. – 734. – P. 219 – 233. 11. 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