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Novel bidentate phosphorus-N-heterocyclic carbine p-cymene type ruthenium complex catalyst as well as preparation method and synthetic application thereof

An azacarbene and p-cymene technology, which is applied in the field of a novel bidentate phosphorus-azacarbene p-cymene-type ruthenium complex catalyst and its preparation, can solve problems such as hindering industrial applications, and achieve simple and easy operation steps The effect of running, air stability, and adaptability to a wide range

Active Publication Date: 2018-08-10
SUN YAT SEN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, these catalytic systems often require higher temperatures (>100 °C) or higher catalyst dosages (>2 mol%), hindering their further industrial applications.

Method used

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  • Novel bidentate phosphorus-N-heterocyclic carbine p-cymene type ruthenium complex catalyst as well as preparation method and synthetic application thereof
  • Novel bidentate phosphorus-N-heterocyclic carbine p-cymene type ruthenium complex catalyst as well as preparation method and synthetic application thereof
  • Novel bidentate phosphorus-N-heterocyclic carbine p-cymene type ruthenium complex catalyst as well as preparation method and synthetic application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Synthesis of the bidentate phosphorus-azaimidazole chloride salt ligand 5a was carried out in accordance with the following steps: 316mg (1.02mmol) o-diphenylphosphine benzyl chloride and 186mg (1.0mmol) 1-metrimethylphenylimidazole were dissolved in 2ml of anhydrous DMF was stirred at 90°C for 48h under the protection of argon. Cool to room temperature, spin dry the solvent, and recrystallize the crude product from dichloromethane-ethyl acetate to obtain 367 mg of white solid, bidentate phosphorus-azimidazolium chloride ligand 5a, with a yield of 74%.

[0053] 1 H NMR (400MHz, DMSO-d 6 )δ9.84(s,1H),7.97(d,J=6.9Hz,2H),7.58–7.49(m,2H),7.42(s,7H),7.24–7.21(m,4H),7.12(s ,2H), 7.00–6.97(m,1H), 5.79(s,2H), 2.31(s,3H), 1.97(s,6H).

[0054] 13 C NMR (101MHz, DMSO-d 6)δ140.1, 138.2, 138.2, 137.9, 136.2, 136.1, 135.0, 134.9, 134.2, 134.1, 133.4, 133.2, 131.1, 130.2, 130.0, 130.0, 129.6, 129.3, 129.2, 129.0, 124. , J=24.2Hz), 20.6, 16.9.

[0055] 31 P NMR (162MHz, DMSO-d ...

Embodiment 2

[0058] Synthesis of bidentate phosphorus-azimidazole chloride salt ligand 5b, specifically according to the following steps:

[0059] According to the synthesis method of ligand 5a in Example 1, 1-me-trimethylphenylimidazole was replaced with 144mg (1.0mmol) 1-phenylimidazole, and other operating conditions were the same as in Example 1. After the reaction, 390mg of white solid was obtained. Namely, the bidentate phosphorus-azaimidazole chloride ligand 5b, and its yield was 86%.

[0060] 1 H NMR (400MHz, DMSO-d 6 )δ9.91(s,1H),8.17(s,1H),7.78(s,1H),7.73–7.66(m,1H),7.66–7.59(m,4H),7.56(t,J=7.1Hz , 2H), 7.46(t, J=7.4Hz, 1H), 7.33(s, 6H), 7.18–7.04(m, 4H), 6.95–6.92(m, 1H), 5.78(s, 2H).

[0061] 13 C NMR (101MHz, DMSO-d 6 ( , J=22.9Hz).

[0062] 31 P NMR (162MHz, DMSO-d 6 ) δ-18.92(s).

[0063] HRMS(ESI,m / z): calcd for C 28 h 24 N 2 P[M-Cl] + 419.16716,found 419.16639.

Embodiment 3

[0065] Synthesis of bidentate phosphorus-azimidazole chloride salt ligand 5c, specifically according to the following steps:

[0066] According to the synthesis method of ligand 5a in Example 1, 82mg (1.0mmol) 1-methylimidazole was used to replace 1-metrimethylphenylimidazole, and other operating conditions were the same as in Example 1. After the reaction, 298mg of white solid was obtained. Namely, bidentate phosphorus-azaimidazole chloride salt ligand 5c, and its yield was 76%.

[0067] 1 H NMR (400MHz, DMSO-d 6 )δ8.92(s,1H),7.54-7.50(m,1H),7.47-7.43(m,2H),7.37(d,J=8.9Hz,2H),7.34-7.28(m,6H),7.02 (t, J=6.7Hz, 4H), 6.89–6.78(m, 1H), 5.57(s, 2H), 3.52(s, 3H).

[0068] 13 C NMR (101MHz, DMSO-d 6 )δ138.0, 137.8, 136.9, 136.5, 136.4, 134.8, 134.7, 134.2, 133.4, 133.2, 131.1, 131.0, 130.1, 129.7, 129.3, 128.9, 128.8, 123.6, 122.1, 51.32 (d1, J = Hz) .

[0069] 31 P NMR (162MHz, DMSO-d 6 )δ-18.90(s).

[0070] HRMS(ESI,m / z): calcd for C 23 h 22 N 2 P[M-Cl] + 357.15151,f...

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Abstract

The invention discloses a novel bidentate phosphorus-N-heterocyclic carbine p-cymene type ruthenium complex catalyst as well as a preparation method and synthetic application thereof. The catalyst isprepared by the following steps: adding silver oxide and a corresponding bidentate phosphorus-aza-imidazole chloride salt ligand into a dichloromethane solution, and performing a reaction for 12-24 hunder the nitrogen protection conditions of avoiding light at room temperature; adding [Ru(p-cymene)Cl2]2 with an equivalent weight of 0.5 times of that of the ligand under nitrogen protection, and performing a reaction for 12-24 h at room temperature; and after the reaction is finished, performing filtration, and performing recrystallization or performing separation by using dichloromethane-methanol through a silica gel column, so as to obtain the bidentate-phosphorus-N-heterocyclic carbine p-cymene type ruthenium complex catalyst. The catalyst provided by the invention can catalyze a ''hydrogen borrowing coupling'' reaction of an alcohol and an aromatic primary amine under basic conditions to obtain a series of valuable N-alkyl compounds; the bidentate phosphorus-N-heterocyclic carbine p-cymene type ruthenium complex catalyst provided by the invention has simple synthetic raw materials, operation steps are easy to implement, and the stability is good; and the ruthenium complex catalyst has the advantages of a wide range of reaction substrates, mild conditions, high efficiency and practicality, and has important application value.

Description

technical field [0001] The invention relates to the technical field of organic synthesis, in particular to a novel bidentate phosphorus-azacarbene p-cymene-type ruthenium complex catalyst and its preparation method and synthesis application. Background technique [0002] N-alkyl compounds are widely used in the fields of medicine, pesticides, dyes and other fine chemicals. The traditional synthesis methods are mainly Hoffmann alkylation reaction and Buchwald-Hartwig reaction, etc., but these methods It needs to use highly toxic organic halogen reagents, and the reaction conditions are harsh, the environment is polluted, and the yield is not high. In recent years, a new method of transition metal complex catalyzed synthesis can use environmentally friendly, cheap and easy-to-obtain alcohols to replace organohalogen reagents, and the reaction conditions are mild, and the selectivity and yield have also been greatly improved. A promising approach. Among them, ruthenium cataly...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C209/18C07C213/02C07C213/08C07D213/74C07C211/48C07C211/52C07C211/58C07C217/58C07B43/04
CPCB01J31/2404B01J2231/4283B01J2531/821C07B43/04C07C209/18C07C213/02C07C213/08C07D213/74C07C211/48C07C211/52C07C211/58C07C217/58
Inventor 柯卓锋黄明刘嘉豪李胤午
Owner SUN YAT SEN UNIV
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