Novel ruthenium complex and method for preparing methanol and diol

A technology for ruthenium complexes and diols, applied in the field of preparing methanol and diols, can solve the problems that metal complexes have no catalytic activity, carbon dioxide has not been effectively utilized, and have no practicality and economic value.

Active Publication Date: 2014-05-07
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Although 1,2-ethylene glycol can be obtained with a selectivity of 99% through the OMEGA process, one disadvantage of this process is that carbon dioxide has not been effectively utilized, and it is released back to the environment after the reaction
However, the market price of dimethyl carbonate is significantly higher than that of methanol, so this catalytic system obviously does not yet have practical and economic value
In addition, those skilled in the art are well aware that when a metal complex is used as a catalyst, the ligand structure used has a great influence on the catalytic activity of the resulting complex; compound has no catalytic activity

Method used

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  • Novel ruthenium complex and method for preparing methanol and diol
  • Novel ruthenium complex and method for preparing methanol and diol
  • Novel ruthenium complex and method for preparing methanol and diol

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Experimental program
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preparation example Construction

[0139] The preparation method of catalyst of the present invention

[0140] Ruthenium catalyst of the present invention can be prepared by following method:

[0141] Under an inert gas atmosphere, such as nitrogen or argon, at 60-120°C, 1 equivalent of a ruthenium metal precursor, such as [RuHCl(CO)(PPh 3 ) 3 ], [RuH 2 (CO)(PPh 3 ) 3 ], RuCl 2 (PPh 3 ) 3 , [RuCl 2 (C 6 h 6 )] 2 , [RuHCl(PPh 3 ) 3 ], Ru(DMSO) 4 Cl 2 , [Ru(cod)Cl 2 ], [Ru(nbd)Cl 2 ] and 1 to 1.2 equivalents of tridentate aminobisphosphorus ligand reacted in a solvent for 0.5-20h in the system. Wherein said DMSO represents dimethyl sulfoxide, cod represents 1,5-cyclooctadiene, and nbd represents norbornadiene.

[0142] The application of catalyst of the present invention

[0143] Catalyst of the present invention, i.e. ruthenium complex can be used for carbonate, comprise cyclic carbonate, polycarbonate and straight-chain carbonate hydrogenation reduction to methanol and other corresponding alc...

Embodiment 1

[0169] Embodiment 1: the preparation of catalyst ruthenium complex 1a

[0170]

[0171] Under an inert gas atmosphere such as nitrogen or argon, add HCl·HN(CH 2 CH 2 PPh 2 ) 2 (1.20g, 2.51mmol), toluene (20mL) and 15% aqueous sodium hydroxide solution (10mL). The reaction mixture was stirred at room temperature until the solids were completely dissolved. The organic phase was separated under inert atmosphere and washed twice with distilled water (2 x 5 mL). The combined aqueous phases were extracted twice with toluene (2 x 10 mL). All organic phases were combined and dried over anhydrous sodium sulfate. After removing the desiccant by filtration, the solvent was removed under reduced pressure in vacuo to obtain the free aminobisphosphorus ligand crude product. This crude product was dissolved in toluene (18 mL) and RuHCl(CO) (PPh 3 ) 3 (2.28g, 2.39mmol), reflux reaction for 2 hours. After the reaction system was cooled to room temperature, hexane (10 mL) was added...

Embodiment 2

[0173] Embodiment 2: the preparation of catalyst ruthenium complex 1b

[0174]

[0175] HN(CH 2 CH 2 P i PR 2 ) 2 (217mg, 0.710mmol) and RuHCl(CO)(PPh 3 ) 3 (644mg, 0.676mmol) was dissolved in toluene (4mL), heated to reflux for 5 hours. After the reaction solution was cooled to room temperature, hexane (6 mL) was added. The precipitated solid was filtered and dried to obtain 288 mg of ruthenium complex 1b with a yield of 90%.

[0176] 1 H NMR (400MHz, CDCl 3 )δ3.50-3.39(m,1H),3.31-3.26(m,2H),2.77-2.65(m,2H),2.35-2.09(m,6H),1.86-1.74(m,2H),1.60- 1.44(m,6H),1.34-1.08(m,18H),-16.30(t,J=19.2Hz,0.12H),-16.54(t,J=18.0Hz,0.88H)ppm; 31 P NMR (161.9MHz, CDCl 3 )δ74.6(s,br)ppm; HRMS(MALDI)m / z calcd.for C 17 h 38 NOP 2 96 Ru:430.1499, Found:430.1502[M-Cl] + ;IR (film) 1973, 1960, 1910cm -1 .

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Abstract

The invention provides a method for preparing methanol and diol from cyclic carbonates and polycarbonates. The method comprises: in hydrogen atmosphere, in an organic solvent, and in the presence of a ruthenium complex (Ru(L)XYY') and an alkali, performing hydrogenation reduction reaction on a cyclic carbonate or a polycarbonate, so as to obtain methanol and diol, wherein all groups in the formula are defined in the specification. The invention also provides the ruthenium complex formed by ruthenium and a tridentate amino diphosphine ligand. The invention also provides a method for preparing deuterated methanol and deuterated diol by employing the above preparation method. The method provided by the invention is high in efficiency, high in selectivity, economic, environment-friendly, and simple for operation, can be performed under mild conditions, and has complete atom economy.

Description

technical field [0001] The present invention relates to the field of organic synthesis. More specifically, the present invention relates to methods for the preparation of methanol and diols using ruthenium complexes as catalysts. Background technique [0002] Methanol is the simplest, safest, and easiest to store and transport liquid oxygenated hydrocarbon fuel. It is also an important chemical raw material that can replace petroleum. It can be used to synthesize a variety of products, such as methanol to olefins (MTO), methanol to propylene (MTP), methanol to aromatics (MTA), etc. As an important energy carrier, methanol is an effective solution to the energy problems caused by the decreasing oil, coal and natural gas resources in the post-oil and gas era [Olah, G.A., Geoppert, A. & Surya Prakash, G.K. Beyond Oil and Gas: The Methanol Economy, Wiley-VCH, 2006.]. In recent years, the production scale of methanol has grown rapidly (in 2010, China produced only 38 million t...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C31/04C07C31/20C07C29/149C07C33/26C07C43/13C07C41/18C07C43/178C07C39/04C07C37/00C07B57/00C07F19/00B01J31/24
CPCC07C31/20C07F15/0046C07C31/04B01J31/24C07C29/136B01J31/2409C07B41/02C07B59/001C07C37/0555C07C41/26C07F15/0053C07C2601/14C07B2200/05B01J2231/641B01J2531/0258B01J2531/821C07C31/202C07C31/205C07C31/207C07C43/1782C07C43/13C07C39/04B01J31/189B01J2231/643B01J2531/0247C07F19/00Y02P20/52B01J31/20B01J2231/64C07C33/26B01J31/2476
Inventor 丁奎岭韩召斌
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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