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Bridged bisamido rare-earth amide compounds, and preparation method and application thereof

A bridging bisamide-based rare earth technology, which is applied in the field of catalysts and their preparation, can solve the problems of poor catalyst regioselectivity, limited catalyst metal types, harsh reaction conditions, etc., and achieve short reaction time, high yield, and easy access to raw materials. The effect

Active Publication Date: 2014-12-03
苏州三木知识产权服务有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

In 2011, their research group directly used cesium carbonate as a catalyst to catalyze the carboxylation reaction of terminal alkyne and carbon dioxide. The reaction can get a higher yield in 14-24 hours, but it needs to be carried out under the harsh conditions of 2.5 atmospheres and 120°C.
[0006] (3) In 2011, Lu, X.B.'s research group used silver iodide to catalyze the carboxylation reaction of terminal alkyne and carbon dioxide, and a higher yield could be obtained at 1mol%, 50°C for 12 hours, but it needed to be in the state of 2 atmospheres conduct
[0010] Although these catalytic systems can catalyze the carboxylation reaction of terminal alkynes and carbon dioxide to obtain alkynoic acid compounds, there are many problems in these systems, such as: poor regioselectivity of catalysts, large amount of catalysts, and limited catalyst metal species. Limits, harsh reaction conditions, poor universality of substrates, etc.

Method used

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  • Bridged bisamido rare-earth amide compounds, and preparation method and application thereof
  • Bridged bisamido rare-earth amide compounds, and preparation method and application thereof
  • Bridged bisamido rare-earth amide compounds, and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0046] Embodiment 1: prepare {LLa[N(SiMe 3 ) 2 ]·THF} 2

[0047] 1) Before preparing the bridged bisamide-based rare earth amides, prepare LH 2 , its preparation method is as follows:

[0048] Synthesis of N,N'-(cyclohexane-1,2-diyl)bis(4-tert-butylbenzamide): weigh a certain molar amount of cyclohexanediamine in a round bottom flask, and measure it at 1.6ml / mmol Dilute sodium hydroxide solution in a round-bottomed flask, then weigh p-tert-butylbenzoyl chloride at a molar ratio of 2:1, slowly drop p-tert-butylbenzoyl chloride into the round-bottomed flask, and react at room temperature After 6 hours, the reaction stopped. Suction filtration with a Buchner funnel, the solid was washed with deionized water until neutral, dried under an infrared lamp, and then recrystallized with anhydrous methanol to obtain compound LH 2 , yield 80%. NMR data: 1 H NMR (400MHz, CDCl 3 ): δ7.71(d, J=8.6Hz, 4H, ArH); 7.39(d, J=8.6Hz, 4H, ArH); 7.00(d, J=6.4Hz, 2H, NH); 3.96(s, 2H, CH); 2....

Embodiment 2

[0053] Embodiment 2: preparation {LNd [N (SiMe 3 ) 2 ]·THF} 2

[0054] Steps (1), (2) and (3) of present embodiment 2 are the same as embodiment 1, wherein the reaction time in step (1) is 9 hours, in step (2) in a dehydration deoxygenation, argon protection Add Nd[N(SiMe 3 ) 2 ] 3 , the ether solvent was changed to diethyl ether, and the reaction time was 20 hours; after the reaction was completed, after post-treatment, the room temperature was left to stand until crystals were precipitated, which was the bridged bisamide-based rare earth aminate {LNd[N(SiMe 3 ) 2 ]·THF} 2 .

[0055] {LNd[N(SiMe 3 ) 2 ]·THF} 2 Data: 88% yield. Elemental analysis: C, 56.40; H, 7.98; N, 5.23; Nd, 17.85. C 76 h 126 N 6 o 6 Nd 2 Si 4 Theoretical: C, 56.32; H, 7.84; N, 5.19; Nd, 17.80. Infrared absorption spectrum data (KBr, cm -1 ): 3439(s), 2963(w), 2359(m), 1635(m), 1541(s), 1384(s), 1240(s), 1216(s), 1156(vs), 504(s ).

Embodiment 3

[0056] Embodiment 3: preparation {LSm [N (SiMe 3 ) 2 ]·THF} 2

[0057] Steps (1), (2) and (3) of present embodiment 3 are the same as embodiment 1, wherein the reaction time in step (1) is 12 hours, in step (2) in a dehydration deoxygenation, inert gas protection Sm[N(SiMe 3 ) 2 ] 3 , the ether solvent is replaced by ethylene glycol dimethyl ether, and the reaction time is 24 hours; after the reaction is completed, after the post-treatment, it is allowed to stand at room temperature until crystals are precipitated, which is the bridged bisamide-based rare earth aminate {LSm[N(SiMe 3 ) 2 ]·THF} 2 .

[0058] {LSm[N(SiMe 3 ) 2 ]·THF} 2 Data: Yield 78%. Elemental analysis: C, 56.05; H, 7.85; N, 5.20; Sm, 18.48. C 76 h 126 N 6 o 6 SM 2 Si 4 Theoretical: C, 55.90; H, 7.78; N, 5.15; Sm, 18.42. Infrared absorption spectrum data (KBr, cm -1 ): 3440(s), 2963(w), 2361(m), 2337(m), 1634(m), 1541(s), 1507(w), 1384(s), 1236(s), 1219(s ), 1157(vs), 555(m), 505(s).

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Abstract

The invention discloses bridged bisamido rare-earth amide compounds, and a preparation method and catalytic application thereof. The general formula of the rare-earth compounds is {LLn[N(SiMe3)2].THF}2, and the chemical structural formula is disclosed in the specification. In the general formula, L represents a bridged bisamido ligand, and the ligand LH2 is N,N'-(cyclohexane-1,2-diyl)bis(4-tert-butylbenzamide); and Ln is a rare-earth metal selected from lanthanum, neodymium, samarium, yttrium or ytterbium. The bridged bisamido rare-earth amide compounds have the advantages of simple synthesis process, definite structure and high yield. The invention also discloses a preparation method of the compounds and an application method of the compounds as a catalyst for catalyzing carboxylation reaction between alkynyl terminal group and carbon dioxide. The application method has the advantages of mild conditions, high activity, favorable selectivity and wide substrate application range.

Description

technical field [0001] The invention relates to a catalyst and its preparation technology, in particular to a bridging bisamide-based rare earth amidate, its preparation method and its application in catalyzing the carboxylation reaction of terminal alkynes and carbon dioxide. Background technique [0002] Alkynoic acids are important intermediates in organic synthesis and have a wide range of uses. For example, alkynoic acid compounds can be used to synthesize some anti-disease (such as: malaria, hepatitis, etc.) drugs. Therefore, alkynoic acid compounds have received more and more attention in recent years. A major method for the synthesis of alkynes is the carboxylation of terminal alkynes with carbon dioxide. At present, some catalysts have been found to have better catalytic effects on this type of reaction, mainly including transition metal compound catalytic systems and organic reagent catalytic systems. [0003] Reports on the catalytic system of transition metal ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/00B01J31/22B01J31/26C07B41/08C07C51/15C07C57/42C07C57/60C07C201/12C07C205/56C07D333/24
Inventor 赵蓓程浩陆澄容
Owner 苏州三木知识产权服务有限公司
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