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Application of amino aryloxy rare-earth metal-lithium amide used as catalyst

An amino aryloxy rare earth, representing amino aryloxy technology, is applied in the field of anionic amino aryloxy rare earth metal amides, and can solve the problem of low catalytic activity of cyclic aliphatic amines and no amino aryloxy rare earth metal- Lithium amide, narrow substrate range, etc., to achieve the effects of good substrate adaptability, short reaction time and mild reaction conditions

Inactive Publication Date: 2012-10-31
SUZHOU UNIV
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AI Technical Summary

Problems solved by technology

[0004] In 2008, Marks reported the neutral trisilicon amine-based rare earth compound Ln[N(TMS) 2 ] 3 (See: Seo, S, Y.; Marks, T. J. Org. Lett. 2008, 10, 317) as a catalyst, catalyzing the amidation reaction of aldehydes and amines under mild conditions, avoiding the traditional harsh reaction conditions, showing The application potential of rare earth metal catalysts in this reaction; however, the catalytic system is suitable for a narrow range of substrates, and the catalytic activity for cyclic aliphatic amines is very low
[0005] So far, among the catalysts reported in the literature to catalyze the amidation reaction of aldehydes and amines, no aminoaryloxy rare earth metal-lithium amides have been reported as catalysts.
At the same time, there is no report on the use of rare earth metal catalysts to catalyze monoaldehydes and diamines to generate bisamides.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0024] Embodiment one: preparation [NO] 2 Pr[N(SiMe 3 ) 2 ] Li 2 (THF) 2 , [NO]=p-X-C 6 h 4 NCH 2 (3-R 2 -5-R 3 -C 6 h 2 -2-O), X is methyl, R 2 , R 3 All are tert-butyl.

[0025] (1) 2.60 g [NO]H 2 (8.00 mmol) dissolved in tetrahydrofuran, adding n BuLi (8.00 mmol) in hexane, stirred at -10°C for one hour, then added Pr[N(SiMe 3 ) 2 ] 3 (μ-Cl)Li(THF) 3 (4.00 millimoles) in tetrahydrofuran (THF), stirred and reacted overnight at 50° C.;

[0026] (2) Remove the solvent, add 50 milliliters of toluene to heat and extract, centrifuge, transfer the supernatant, add 6.00 milliliters of hexane, concentrate the solution to 18 milliliters, room temperature overnight, separate out 3.54 grams (3.20 mmoles) of blue crystals, and the yield is 80 %. Melting point: 212-214 °C. Elemental analysis: C, 62.90; H, 8.50; N, 3.54; Pr, 12.75. Infrared spectrum (KBr, cm -1 ): 3327(s), 2956(s), 2866(s), 1616(s), 1516(s), 1469(s), 1359(m), 1240(s), 1176(s), 985(w ), 931(m), 8...

Embodiment 2

[0027] Embodiment two: preparation [NO] 2 Pr[N(SiMe 3 ) 2 ] Li 2 (THF) 2 , [NO]=p-X-C 6 h 4 NCH 2 (3-R 2 -5-R 3 -C 6 h 2 -2-O), X is fluorine, R 2 , R 3 All are tert-butyl.

[0028] (1) 2.05 g of [NO]H 2 (6.20 mmol) dissolved in tetrahydrofuran, adding n BuLi (6.20 mmol) in hexane, stirred at -10°C for one hour, then added Pr[N(SiMe 3 ) 2 ] 3 (μ-Cl)Li(THF) 3 (3.10 mmol) in tetrahydrofuran solution, 50 DEG C stirred and reacted overnight;

[0029] (2) Remove the solvent, add 30 milliliters of toluene to heat and extract, centrifuge, transfer the supernatant, add 5.00 milliliters of hexane, concentrate the solution to 10 milliliters, leave at room temperature overnight, and precipitate 2.87 grams (2.57 mmoles) of blue crystals, yield 83 %. Melting point: 230-234 °C. Elemental analysis: C, 60.30; H, 7.69; N, 3.74; Pr, 12.70. Infrared spectrum (KBr, cm -1): 3318(s), 2959(s), 2866(s), 1606(s), 1516(s), 1468(s), 1367(m), 1222(s), 1163(s), 931(m ), 827(m). ...

Embodiment 3

[0030] Embodiment three: preparation [NO] 2 Pr[N(SiMe 3 ) 2 ] Li 2 (THF) 2 , [NO]=p-X-C 6 h 4 NCH 2 (3-R 2 -5-R 3 -C 6 h 2 -2-O), X is chlorine, R 2 , R 3 All are tert-butyl.

[0031] (1) 2.50 g of [NO]H 2 (7.25 mmol) dissolved in tetrahydrofuran, adding n BuLi (7.25 mmol) in hexane, stirred at -10°C for one hour, then added Pr[N(SiMe 3 ) 2 ] 3 (μ-Cl)Li(THF) 3 (3.62 millimoles) in tetrahydrofuran solution, 50 ℃ of stirring reaction overnight;

[0032] (2) Remove the solvent, add 30 milliliters of toluene to heat and extract, centrifuge, transfer the supernatant, add 4.00 milliliters of hexane, concentrate the solution to 12 milliliters, leave at room temperature overnight, and precipitate 3.41 grams (2.97 mmoles) of blue crystals, yield 82 %. Melting point: 188-191 °C. Elemental analysis: C, 58.30; H, 7.72; N, 3.81; Pr, 12.20. Infrared spectrum (KBr, cm -1 ): 3318(s), 2960(s), 2866(s), 1664(s), 1501(s), 1468(s), 1367(m), 1234(s), 1176(s), 987(w ), 82...

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Abstract

The invention discloses application of amino aryloxy rare-earth metal-lithium amide used as a catalyst to catalyze amidation reaction of aldehyde and amine to prepare acid amide or bisamide. A general formula of the amino aryloxy rare-earth metal-lithium amide is [NO]2Ln[N(TMS)2][Li9(THF)]2; in the formula, [NO] represents amino aryloxy ligand; X is selected from one of hydrogen, C1-C4 saturated alkyl or halogen; R2 and R3 are respectively selected from one of methyl or tertiary butyl; Ln represents a central ion and is selected from one of praseodymium, neodymium, samarium, ytterbium or yttrium, and TMS (tetramethylsilane) is tetramethylsilane. The complex is used as the catalyst for catalyzing the aldehyde and amine to synthetize the acid amide. The dosage of the catalyst is less, the reaction condition is mild and the reaction time is short.

Description

technical field [0001] The present invention relates to an anionic amino aryloxy rare earth metal amidate, in particular to an amino aryloxy rare earth amidate whose complex lithium center ion is trivalent and its preparation as a catalyst to catalyze the amidation reaction of aldehyde and amine Applications of amides and bisamides. Background technique [0002] Aromatic and aliphatic amides are a class of functional groups with important application value. They are widely found in polymers, natural products and pharmaceuticals. The formation of amide bonds is one of the most important reactions in organic synthetic chemistry. Therefore, the study of its synthesis has important application value. [0003] The traditional catalyzed synthesis of amides from aldehydes and amines requires harsh conditions, such as the combined action of oxidants iodine and hydrogen peroxide (see: Jie, J.; Fang, J, M. J. Org. Chem. 2003, 68, 1158) , nitrogen heterocyclic carbene and strong base...

Claims

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Application Information

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IPC IPC(8): B01J31/22C07C231/10C07C233/65C07C233/75C07C233/66C07C235/46C07D295/192C07B43/06
Inventor 姚英明王超黄玲玲沈琪
Owner SUZHOU UNIV
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