Chin. J. Org. Chem. ›› 2018, Vol. 38 ›› Issue (8): 2017-2027.DOI: 10.6023/cjoc201804023 Previous Articles     Next Articles



蔡涛, 杨玉, 张丽, 温庭斌   

  1. 厦门大学化学化工学院化学系 厦门 361005
  • 收稿日期:2018-04-13 修回日期:2018-05-14 发布日期:2018-05-17
  • 通讯作者: 温庭斌
  • 基金资助:


Reactivity of Ruthenium Allenylidene Complexes with Hydrazines:Formation of Acrylonitrile Complexes

Cai Tao, Yang Yu, Zhang Li, Wen Tingbin   

  1. Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005
  • Received:2018-04-13 Revised:2018-05-14 Published:2018-05-17
  • Contact: 10.6023/cjoc201804023
  • Supported by:

    Project supported by the National Basic Research Program of China (973 Program, No. 2012CB821600) and the Program for Changjiang Scholars and Innovative Research Team in University (No. IRT_17R65).

The cationic ruthenium allenylidene complexes[RuCl(=C=C=CR2)(DPPQ)2] [BPh4] (3a:R=Ph; 3b:CR2=FN=9H-fluoren-9-ylidene) supported by the heterobidentate P,N-donor ligand 8-(diphenylphosphanyl)quinoline (DPPQ) have been synthesized from the reactions of the dimeric complex[Ru(μ-Cl)(DPPQ)2]2[BPh4]2 (1) with excess 1,1-diphenylprop-2-yn-1-ol (2a) or 9-ethynyl-9H-fluoren-9-ol (2b), respectively. Addition of hydrazines to the ruthenium-allenylidenes 3 led to the facile formation of ruthenium-bound acrylonitrile complexes[RuCl(N≡C-CH=CR2)(DPPQ)2] [BPh4] (4a:R=Ph; 4b:CR2=FN) at room temperature. This reaction involves the intermolecular nucleophilic attack of hydrazines at the Cα atom of the allenylidene ligand, which represents the first examples of addition of hydrazines to metal-allenylidenes affording acrylonitrile derivatives. Reaction of acrylonitrile complex 4 with an excess of propargyl alcohols 2a or 2b (4 equiv.) could release the organic acrylonitriles 3,3-diphenylacrylonitrile (5a) or 2-(9H-fluoren-9-ylidene)-acetonitrile (5b) along with regeneration of allenylidene complex 3. In addition, the catalytic activity of 1 for the transformation of terminal propargyl alcohols and hydrazines into acrylonitriles has been investigated preliminarily. The results showed that the catalytic reaction did proceed to give the desired acrylonitrile products, albeit the yield not good. Nevertheless, our results of the catalytic reactions demonstrated that it is very promised to develop new catalytic reactions for the transformation of terminal propargylic alcohols and hydrazines into acrylonitriles via allenylidene intermediates.

Key words: ruthenium, allenylidene, alkyne, hydrazine, nitrile