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Salalen-type rare-earth metal amide as well as preparation method and application thereof

A rare earth metal and amide technology, applied in the direction of organic chemistry, can solve the problems of rare rare earth metal complexes and other problems, and achieve the effects of convenient separation and purification, clear structure and simple synthesis

Inactive Publication Date: 2013-05-08
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0015] However, so far, there have been no reports of rare earth metal complexes with Salalen as a ligand

Method used

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  • Salalen-type rare-earth metal amide as well as preparation method and application thereof
  • Salalen-type rare-earth metal amide as well as preparation method and application thereof
  • Salalen-type rare-earth metal amide as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Example 1: Preparation of SalalenH 2 (R 1 =R 2 = Bu t )

[0050] Add 4.68 grams (20 mmoles) of 3,5-di-tert-butyl salicylaldehyde into a two-necked bottle with a stirring bar,

[0051] Add methanol to dissolve, drop two drops of glacial acetic acid, then add 1.8mL (20 mmol) of N-methylethylenediamine, stir for half an hour, then add 4.12 g (20 mmol) of 2,4-di-tert-butylphenol ), 0.9 g (30 mmol) of paraformaldehyde, reacted at 65-75° C. for 12 hours, a large amount of yellow solids precipitated, filtered with suction, washed the filter cake with methanol, and drained, the yield was 80%. NMR data: 1 H NMR (400MHz, CDCl 3 ): 8.37(s, 1H), 7.38(d, 1H), 7.20(d, 1H), 7.07(d, 1H), 6.82(d, 1H), 3.77(t, 2H), 3.74(s, 2H) , 2.84(t, 2H), 2.38(s, 3H), 1.44(s, 9H), 1.37(s, 9H), 1.30(s, 9H), 1.27(s, 9H).

Embodiment 2

[0052] Example two: (Salalen)Y[N(SiMe 3 ) 2 ](THF)

[0053] Y[N(SiMe 3 ) 2 ] 3 (μ-Cl)Li(THF) 3 (2.89 mmol) THF solution was added to SalalenH 2 (1.47 grams, 2.89 mmol) in the tetrahydrofuran solution, the system turns light yellow transparent solution from bright yellow, 25 DEG C of stirring reaction about 2 hours, remove tetrahydrofuran, add 20 milliliters of normal hexanes and extract twice, centrifuge and remove a little precipitation, The supernatant was transferred, concentrated, and left overnight at room temperature, and 1.91 g of light yellow crystals were precipitated, with a yield of 80%. Elemental analysis: C, 62.09; H, 9.43; N, 5.25; Y, 10.98; C 43 h 76 N 3 o 3 Si 2 Theoretical values ​​for Y: C, 62.36; H, 8.25; N, 5.07; Y, 10.74. 1 H NMR (400MHz, C 6 D. 6 , 25°C): δ7.71(d, J=2.5Hz, 1H, ArH), 7.50(d, J=2.4Hz, 1H, ArH), 7.26(s, 1H, N=CHAr), 6.96(d , J=2.3Hz, 1H, ArH), 6.89(d, J=2.5Hz, 1H, ArH), 4.37(d, J=12.7Hz, 1H, ArCH 2 N), 3.58 (br, 4H, α-CH 2 T...

Embodiment 3

[0054] Embodiment three: (Salalen)Sm[N(SiMe 3 ) 2 ](THF)

[0055] Sm[N(SiMe 3 ) 2 ] 3 (μ-Cl)Li(THF) 3 (2.82 mmol) THF solution was added to SalalenH 2 (1.44 g, 2.82 mmol) in THF solution, the system changed from bright yellow to yellow solution, and stirred at 25°C for about 2 hours, removed THF, added 20 ml of n-hexane for extraction twice, centrifuged to remove a little precipitate, and the supernatant After transferring, concentrating, overnight at room temperature, 1.86 g of yellow crystals were precipitated, with a yield of 74%. Elemental analysis: C, 58.36; H, 8.80; N, 4.07; Sm, 16.79;

[0056] C 43 h 76 N 3 o 3 Si 2 Theoretical values ​​for Sm: C, 58.06; H, 8.61; N, 4.72; Sm, 16.90. Infrared absorption spectrum data: 2960s, 2900s, 2869s, 1620s, 1540m, 1470s, 1440s, 1410m, 1360mm, 1310m, 1250m, 1200w, 1160m, 928m, 877m, 839s, 742w, 617w.

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Abstract

The invention discloses Salalen-type rare-earth metal amide as well as a preparation method and catalytic application thereof. The general formula of the amid is (Salalen)Ln(NR2)(THF). The Salalen-type rare-earth metal amide disclosed by the invention is simple in synthesis, convenient to separate and purify and clear in structure and has high yield. The Salalen-type rare-earth metal amide provided by the invention serving as a catalyst also has good controllability and selectivity in the aspect of catalyzing ring-opening polymerization of racemization lactide and can be used for preparing a high-heterotactic polymer with moderate distributed high-molecular weight.

Description

technical field [0001] The invention relates to the field of catalysts, in particular to a Salalen-type rare earth metal amidide and a preparation method and application thereof. Background technique [0002] Salen and Salan-type metal complexes have been widely used to catalyze polymerization and organic reactions, and recently, half-Salan structure, half-Salen structure Salalen-type ligands have attracted people's attention. Salalen-type ligands can first form half of the Salen structure through the condensation of salicylaldehyde with substituents and amines, and then Mannich reactions with phenols and paraformaldehyde with equimolar amounts of substituents or in the presence of triethylamine. 2,4-Dialkyl-6-chloromethylphenol undergoes a condensation reaction to synthesize the other half of the Salan structure. Such a type of ligand integrates rigid and flexible bridges, and the corresponding metal complexes may exhibit different catalytic properties from Salan and Salen...

Claims

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Application Information

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IPC IPC(8): C07F19/00C08G63/08C08G63/84
Inventor 姚英明聂昆
Owner SUZHOU UNIV
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