Ruthenium Complex Synthesis via Dimer and Primary Alcohol
Solution Overview
Problem
The existing methods for producing {bis[2-(diphenylphosphino)ethyl]amine}carbonylhalohydridoruthenium(II) result in low atom efficiency of the ruthenium source, produce difficultly-removable by-products, and yield a mixture of isomers, leading to decreased efficiency in hydrogenation reactions.
Innovation Solution
Reacting dichloro(p-cymene)ruthenium(II) dimer with bis[2-(diphenylphosphino)ethyl]amine in the presence of a primary alcohol and a base to obtain the ruthenium complex as a single isomer with high atom efficiency, eliminating the need for triphenylphosphine and simplifying the purification process.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Loss of substance
If carbonylchlorohydridotris(triphenylphosphine) ruthenium(II) is used as a ruthenium source, then the ruthenium complex can be produced, but the atom efficiency is very low (17.3 mass%) and 3 equivalents of triphenylphosphine are produced as difficultly-removable by-products
Solution Approach 1:
The invention extracts and removes the problematic triphenylphosphine ligand from the ruthenium source complex, replacing it with a ruthenium source that does not contain phosphine ligands. This eliminates the generation of difficultly-removable by-products and improves atom efficiency by ensuring all ruthenium atoms in the source are incorporated into the final product.
Solution Approach 2:
The invention changes the chemical composition parameters of the ruthenium source from carbonylchlorohydridotris(triphenylphosphine) ruthenium(II) to dichloro(p-cymene)ruthenium(II) dimer. This parameter change transforms the ruthenium source from one that generates harmful by-products to one that provides high atom efficiency and easy-to-remove by-products.
2Manufacturing precision
If the conventional production method is used, then the ruthenium complex can be obtained, but the obtained product is a mixture of isomers requiring complex purification
Solution Approach 1:
Instead of obtaining a mixture of isomers and then separating them through complex purification, the invention inverts the approach by using specific reaction conditions and a primary alcohol solvent that directly favor the formation of the desired single isomer. This eliminates the need for complex purification processes while achieving high isomer purity.
3Manufacturing precision
If washing with n-hexane and ethanol is performed to isolate single isomer, then isomer purity is improved, but the yield decreases from 85% to 55%
Solution Approach 1:
The invention performs preliminary action by designing the reaction system from the outset to produce the desired single isomer directly, rather than producing a mixture and then separating it. By using a primary alcohol as solvent and a base, the reaction selectively forms the desired isomer, eliminating the need for yield-reducing purification steps.
Applied Scientific Principles
This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.
Function Achieved in This Case
This method achieves a high yield of the ruthenium complex as a single isomer with improved atom efficiency, eliminating difficultly-removable by-products and maintaining high catalytic activity in hydrogenation reactions.
Implementation Method 1
reacting dichloro(p-cymene)ruthenium(II) dimer with bis[2-(diphenylphosphino)ethyl]amine in the presence of a primary alcohol and a base to obtain the ruthenium complex
Implementation Method 2
exhibits excellent catalytic activity in a hydrogenation reaction of various carbonyl compounds such as ketones, esters and lactones and gives alcohols efficiently
Implementation Method 3
hydrogenation reaction of various carbonyl compounds such as ketones, esters and lactones and gives alcohols efficiently
Data Source
AI summary
The present invention relates to a method for efficiently producing a ruthenium complex (1A) by reacting a dinuclear ruthenium complex (2A) with a compound (3A) in the presence of a primary alcohol and a base. The ruthenium complex (1A) can also be efficiently produced by treating a dinuclear ruthenium complex (4A) with a primary alcohol and a base. (In the formulas, solid lines, triple lines, broken lines, C, H, N, OP, Ru, X, AH and R1 to R12 have the meanings defined in the specification.)