Tetraphosphite ligand for ultrafast isomerization-hydroformylation of C4 raffinate under mild conditions

Zhang，Runtong1; Yan，Xin1; Guan，Fanfu1; Qian，Yu1; Peng，Jianghua1; Wang，Jianxin1; Ma，Baode1; Bai，Shao Tao1,2; Wen，Jialin1,2; Zhang，Xumu1

2022-09-01

10.1016/j.jcat.2022.06.009

JOURNAL OF CATALYSIS   Impact Factor & Quartile

0021-9517

1090-2694

Ultrafast linear selective isomerization-hydroformylation (ISO-HF) tandem reaction under mild conditions remains a challenge. Herein, a novel tetraphosphite ligand (TBTP) and its application in ISO-HF of C4 Raffinate were reported. Based on a biphenol-2,2',6,6'-tetraol with sterically demanding tert-butyl substituents, TBTP can be readily prepared by the reaction of biphenyl phosphorchloridite and tetraol in kilogram scale. The structural and coordinating features of this ligand and its rhodium complex were studied by XRD, NMR and DFT calculations. This tetraphosphite ligand showed high turnover frequencies and regioselectivities in the rhodium-catalyzed ISO-HF of trans-, cis-2-butene. Such hydrolytically stable ligand was successfully applied in the ISO-HF of etherified C4 feed under a mild condition (65 degrees C, 7 bar syngas, TOF up to 1574 h(-1), similar to 95% linear selectivity). An over-14-day durability test that was operated in two 5-L continuously stirred-tank reactors (CSTRs) in series delivered 79 kg n-valeraldehyde for the manufacture of C10 plasticizer DPHP. (C) 2022 Elsevier Inc. All rights reserved.

Isomerization Hydroformylation C4 raffinate Tetraphosphite N-valeraldehyde

SCI ; EI

English

First ; Corresponding

Technology Innovation Committee of Shenzhen[JCYJ20170817104824122] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry ; Engineering

Chemistry, Physical ; Engineering, Chemical

WOS:000829348000007

ACADEMIC PRESS INC ELSEVIER SCIENCE

20222812355723

Design for testability ; Durability ; Hydroformylation ; Isomers ; Ligands ; Rhodium compounds

Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Products Generally:804

CHEMISTRY

2-s2.0-85133884910

Web of Science

1.Guangdong Provincial Key Laboratory of Catalysis,Department of Chemistry,Southern University of Science and Technology,Shenzhen,518055,China
2.Academy for Advanced Interdisciplinary Studies,Southern University of Science and Technology,Shenzhen,518055,China

Zhang，Runtong,Yan，Xin,Guan，Fanfu,et al. Tetraphosphite ligand for ultrafast isomerization-hydroformylation of C4 raffinate under mild conditions[J]. JOURNAL OF CATALYSIS,2022,413:388-397.

Zhang，Runtong.,Yan，Xin.,Guan，Fanfu.,Qian，Yu.,Peng，Jianghua.,...&Zhang，Xumu.(2022).Tetraphosphite ligand for ultrafast isomerization-hydroformylation of C4 raffinate under mild conditions.JOURNAL OF CATALYSIS,413,388-397.

Zhang，Runtong,et al."Tetraphosphite ligand for ultrafast isomerization-hydroformylation of C4 raffinate under mild conditions".JOURNAL OF CATALYSIS 413(2022):388-397.