A kind of double metallocene based rare earth guanidinium compound and its preparation method and the preparation method of hydroxy phosphite compound

A technology of hydroxyphosphite and compounds, which is applied in the field of rare earth metal catalyst preparation, can solve the problems that have not been reported yet, and the research scope is narrow.

Inactive Publication Date: 2015-09-30
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the scope of research on the catalytic performance of rare earth metal guanidinium complexes is still very narrow, and there is no report on the addition reaction of aldehydes and phosphites catalyzed by rare earth metal guanidinium complexes.

Method used

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  • A kind of double metallocene based rare earth guanidinium compound and its preparation method and the preparation method of hydroxy phosphite compound
  • A kind of double metallocene based rare earth guanidinium compound and its preparation method and the preparation method of hydroxy phosphite compound
  • A kind of double metallocene based rare earth guanidinium compound and its preparation method and the preparation method of hydroxy phosphite compound

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preparation example Construction

[0035] The technical scheme adopted in the present invention is: a kind of preparation method of double metallocene-based rare earth guanidine complex, comprising the following steps:

[0036] a) Under anhydrous and oxygen-free conditions, in an inert atmosphere, the bridged biguanide and n-butyllithium were reacted in a solvent at 0°C for 2 hours at a molar ratio of 1:2 to obtain a bridged biguanide lithium salt;

[0037] b) Add (R'C to the bridged biguanide lithium salt obtained in step a) 5 h 4 ) 2 Solution of LnCl, continue to react for 12 hours, the reaction temperature is 10-90°C; and the boiling point of the solvent is not exceeded; wherein Ln is ytterbium, erbium, yttrium or samarium;

[0038] Wherein, the general formula of the bridged biguanide is {[H(RN) 2 CN(CH 2 ) 2 ]} 2 And have the structure shown in formula II, wherein R is isopropyl or cyclohexyl; Its synthetic method can refer to literature: Zhang, W.X.; Nishiura, M.; Hou, Z.M.Chem.Eur.J.2007,13,4037, ...

Embodiment 1

[0063] prepare {(C 5 h 5 ) 2 Yb[( i PrN) 2 CN(CH 2 ) 2 ]} 2 :

[0064] At 0°C, slowly add 3.94 mmoles of n-butyllithium hexane solution dropwise to a tetrahydrofuran solution (1.97 mmoles) containing piperazinyl-bridged biguanide, react for 2 hours, then add (C 5 h 5 ) 2 YbCl (3.94 mmol), reacted overnight at 25°C, removed THF, added toluene for extraction, centrifuged to remove lithium chloride, concentrated, and stood at room temperature, 1.56 g (1.65 mmol) of brick red crystals were precipitated, with a yield of 84%. Decomposition temperature: 130-132°C. Elemental analysis: C, 48.47; H, 5.92; N, 9.03; Yb, 36.82. Infrared absorption spectrum data: 2966s, 2927w, 2854w, 1624s, 1458m, 1385s, 1362s, 1257s, 1165s, 1134m, 1065w, 1007m, 933m, 852w, 733w, 548w. The above data prove that the compound was successfully prepared.

Embodiment 2

[0066] prepare {(C 5 h 5 ) 2 Er[( i PrN) 2 CN(CH 2 ) 2 ]} 2 :

[0067] At 0°C, slowly add 3.94 mmoles of n-butyllithium hexane solution dropwise to a tetrahydrofuran solution (1.97 mmoles) containing piperazinyl-bridged biguanide, react for 2 hours, then add (C 5 h 5 ) 2ErCl (3.94 mmol), reacted overnight at 25°C, removed THF, added toluene for extraction, centrifuged to remove lithium chloride, concentrated, and stood at room temperature, 1.50 g (1.62 mmol) of pink crystals were precipitated, with a yield of 82%. Decomposition temperature: 138-140°C. Elemental analysis: C, 48.48; H, 5.97; N, 8.91; Er, 35.85. Infrared absorption spectrum data: 2966s, 2927w, 2858w, 1624s, 1458m, 1389s, 1362s, 1257s, 1165s, 1134m, 1061w, 1003m, 933m, 841w, 737w, 555w. The above data prove that the compound was successfully prepared.

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Abstract

The invention provides a bimetallic cyclopentadienyl rare earth guanidino compound which has a structure as shown in a formula I, wherein the bimetallic cyclopentadienyl rare earth guanidino compound has a general formula of {(R'Cp)2Ln[(RN)2CN(CH2)2]}2, and Ln is a rare earth metal and is selected from one of ytterbium, erbium, yttrium or samarium; R is selected from one of isopropyl and cyclohexyl; and R' is selected from one of H, CH3, But or SiMe3. The bimetallic cyclopentadienyl rare earth guanidino compound has high catalytic activity, and can catalyze the addition of aromatic aldehyde and phosphite. The invention also provides a method for preparing the bimetallic cyclopentadienyl rare earth guanidino compound, and a method for preparing a hydroxyl phosphite compound by taking the bimetallic cyclopentadienyl rare earth guanidino compound as a catalyst.

Description

technical field [0001] The invention relates to the field of preparation of rare earth metal catalysts, in particular to a preparation method of a double metallocene-based rare earth guanidinium compound and a preparation method of hydroxy phosphite compounds. Background technique [0002] Guanidine has three nitrogen atoms with electron-donating ability, and the guanidine anion has a variety of resonance structures, which can coordinate with metals in various ways; at the same time, its steric hindrance and charge effect can be easily regulated by substituents on the nitrogen atom. . Therefore, the guanidinium monoanionic ligand is a very good auxiliary ligand for the synthesis of rare earth metal complexes. Now a variety of single-anion guanidinium-stabilized rare earth metal complexes have been synthesized, such as the corresponding rare earth metal amides, alkyl compounds, hydrides and borohydrides. [0003] Arnold et al. synthesized the monoguanidinium rare earth meta...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F17/00B01J31/22C07F9/40C07F9/655
Inventor 姚英明聂昆刘承伟
Owner SUZHOU UNIV
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