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Novel iridium complex, method for alpha-alkylation of amide by primary alcohol, and application of novel iridium complex

An alkylation and complex technology, applied in chemical instruments and methods, preparation of organic compounds, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as inconvenient experimental operation

Inactive Publication Date: 2014-06-18
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

But this method has the following defects: (1) need to use unfriendly halogenated hydrocarbons as reaction raw materials; (2) this reaction generates a large amount of inorganic salt by-products, and the subsequent treatment in industrial plants will cause additional economic burden and environmental pressure; (3) the reaction needs to be carried out step by step, first at low temperature (usually -78 ℃), using a super base, such as an organolithium reagent, to react with an amide to generate a carbanion, and then react with a halogenated Hydrocarbons react, which brings a lot of inconvenience to the experimental operation
So far, direct alkylation of amides without active α-H using primary alcohols as starting materials has not been reported.

Method used

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  • Novel iridium complex, method for alpha-alkylation of amide by primary alcohol, and application of novel iridium complex
  • Novel iridium complex, method for alpha-alkylation of amide by primary alcohol, and application of novel iridium complex
  • Novel iridium complex, method for alpha-alkylation of amide by primary alcohol, and application of novel iridium complex

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preparation example Construction

[0095] The preparation method of iridium metal complex of the present invention

[0096] The iridium metal complex of the present invention can be prepared by the following methods:

[0097] Under an inert gas atmosphere, such as nitrogen or argon, the iridium metal precursor, such as [Ir(COE) 2 Cl] 2 Ligand PN 3 P is prepared by reacting in a solvent.

[0098] Main advantage of the present invention:

[0099] 1. The iridium metal complex of the present invention has high activity and good stability;

[0100] 2. Using the iridium metal complex of the present invention as a catalyst, primary alcohols can be efficiently used to carry out α-alkylation of amides;

[0101] 3. The raw materials of the inventive method are easy to get, simple to prepare, easy to operate, and low in cost;

[0102] 4. The by-product of the present invention is only water, which is environmentally friendly.

Embodiment 1

[0111] Embodiment 1. Preparation of Complex 1

[0112]

[0113] Under argon protection, add 2.5mmol of ligand PN to a 50ml Schlenk bottle 3 P and 1.25mmol of [Ir(COE) 2 Cl] 2 , and added 30ml of toluene, stirred and reacted at room temperature for 4 hours, a large amount of red solid was generated, the reaction solution was filtered, and the obtained solid was washed 3 times with 2ml of n-hexane, then vacuum dried overnight to obtain 1.7g of Complex 1, yield 90%.

[0114] Complex 1: red solid, yield 90%, 1 H MNR (400MHz, CDCl 3 )δ 9.13(br,1H,NH),7.93(br,1H,NH),7.35(d,J=7.2Hz,2H,py),6.80(m,1H,py),4.05(d,J=8.0 Hz,2H),2.38(d,J=12.8Hz,2H),1.80-1.65(m,4H),1.63-1.21(m,6H),1.42(d,J=13.6Hz,36H); 13 C NMR (100MHz, CDCl 3 )δ 163.6, 140.8, 98.5, 52.9, 40.2, 34.9, 32.3, 30.0, 26.5; 31 P NMR (162MHz, CDCl 3 ): δ 100.7, 90.0 (two groups of double peaks; J=100.7Hz). C 29 h 55 ikB 3 P 2 Elemental analysis is (unit: mass fraction / %, brackets are calculated values): C47.75 (47....

Embodiment 2

[0116] Embodiment 2. Preparation of complex 8

[0117]

[0118] Under the protection of argon, add 0.20 mmol of complex 1 and 0.31 mmol of potassium tert-butoxide to a 10 ml Schlenk bottle, and add 5 ml of benzene, stir and react at room temperature for 1 hour, filter and vacuum the obtained filtrate Filter and wash with n-hexane to finally obtain 90 mg of a dark red solid with a yield of 65%.

[0119] Complex 8: dark red solid, yield 65%. 1 H HMR (400MHz, C 6 D. 6 )δ 6.90(m,1H),6.76(d,J=8.4Hz,1H),5.22(d,J=7.2Hz,1H),4.64(br,1H,NH),4.07(s,2H),2.49 (d,J=8.0Hz,2H),1.79-1.62(m,6H),1.60-1.28(m,4H),1.51(d,J=12.4,18H),1.10(d,J=12.4Hz,18H ); 13 C NMR (100MHz, C 6 D. 6 )δ 175.6, 160.2, 138.2, 104.8 (d, J=10.5Hz), 83.4 (d, J=6.0Hz), 47.5, 39.9, 38.4, 35.9, 32.8, 29.6, 29.3, 27.1. 31 P NMR (162MHz, C 6 D. 6 )δ 89.8,85.6 (two groups of double peaks, J=250Hz).C 29 h 54 IrN 3 P 2 Elemental analysis is (unit: mass fraction / %, brackets are calculated values): C50.21 (49.84), ...

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Abstract

The invention provides a novel iridium metal complex formed through coordination of a tridentate ligand PN<3>P. The iridium metal complex has a high activity and a good stability. Alpha-alkylation of amide can be directly carried out by efficiently using primary alcohol as a raw material with the iridium metal complex as a catalyst. The method has the advantages of easily available raw material, simple preparation, convenient operation, low cost and compatibility of a plurality of substrates with function groups, and is an environmentally-friendly method for the simple preparation of amide and the alpha-alkylation of amide compounds.

Description

technical field [0001] The present invention relates to the field of metal catalysts. More particularly, the present invention relates to novel iridium complexes and methods and uses for alpha-alkylating amides using the complexes with primary alcohols. Background technique [0002] Amides have great application value in the synthesis of natural products and bioactive substances. The α-alkylation of amides is an important method to establish new carbon-carbon bonds, which is of great significance in the synthesis of natural products and biologically active substances and in the modification of proteins. [1] . The approach traditionally employed is the α-alkylation of amides by the reaction of amide-generated enolates and halohydrocarbons in situ. But this method has the following defects: (1) need to use unfriendly halogenated hydrocarbons as reaction raw materials; (2) this reaction generates a large amount of inorganic salt by-products, and the subsequent treatment in i...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00B01J31/24C07B37/04C07C231/12C07C233/11C07C233/08C07C233/05C07C235/34C07D307/54C07D213/56C07D295/182
Inventor 黄正郭乐
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI