Ru-Catalyzed Domino Esterification via Phosphine Ligands

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Solution Overview

Problem

Existing processes for converting olefins to carboxylic acids or esters require intermediate isolation and do not directly form esters with the alcohol part having one more carbon than the employed olefin, limiting efficiency and selectivity.

Innovation Solution

A Ru-catalysed domino hydroformylation/hydrogenation/esterification process using phosphine ligands, where an ethylenically unsaturated compound is converted directly into an ester or diester by charging a ruthenium compound, a phosphine ligand, an acidic compound, and CO, with optional hydrogenation and heating, without isolating intermediates.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If a traditional process for converting olefins to carboxylic acids or esters is used, then the conversion can be achieved, but intermediate isolation is required which reduces efficiency and increases process complexity

Engineering Contradiction:

Improveconversion efficiencyVSAvoidprocess complexity

Core Design Contradiction:

ProductivityVSDevice complexity

Solution Approach 1:

The patent combines hydroformylation, hydrogenation, and esterification into a single integrated catalytic system using a ruthenium complex with phosphine ligand and acidic compound. This merging of three separate processes into one domino reaction eliminates the need for intermediate isolation steps, directly converting olefins to esters in a single operational sequence, thereby improving productivity while reducing process complexity

Inventive Principle:

Principle #5Merging (Combining)

Solution Approach 2:

The patent implements a continuous domino reaction sequence where the product of one reaction immediately becomes the substrate for the next reaction without interruption or isolation. The hydroformylation product (aldehyde) is continuously hydrogenated to alcohol, which is then continuously esterified with the acidic compound, maintaining continuous useful action throughout the process to eliminate downtime and intermediate handling

Inventive Principle:

Principle #20Continuity of useful action

2Manufacturing precision

If existing catalytic systems are used, then olefin conversion can occur, but regioselectivity is insufficient to directly form esters with the desired carbon structure

Engineering Contradiction:

ImproveregioselectivityVSAvoidprocess simplicity

Core Design Contradiction:

Manufacturing precisionVSEase of manufacture

Solution Approach 1:

The patent employs specific parameter changes in the catalytic system, including using a ruthenium complex with particular phosphine ligands (formula I) and acidic compounds (formula IIa or IIb), along with specific reaction conditions (temperature range 50-180°C, pressure conditions for CO and H2). These parameter optimizations enable high regioselectivity for forming esters where the alcohol part has one more carbon than the employed olefin, achieving manufacturing precision without complicating the overall process

Inventive Principle:

Principle #35Parameter changes

3Productivity

If multiple reaction steps are performed separately, then each reaction can be optimized, but the overall process becomes less efficient and requires intermediate isolation

Engineering Contradiction:

Improveoverall process efficiencyVSAvoidtime for intermediate isolation

Core Design Contradiction:

ProductivityVSLoss of time

Solution Approach 1:

The patent merges hydroformylation, hydrogenation, and esterification into a single pot reaction using a ruthenium-catalyzed domino process. This eliminates the time required for intermediate isolation and multiple setup/teardown cycles, directly converting olefins to esters in one continuous operation, thereby improving overall process efficiency and eliminating time losses

Inventive Principle:

Principle #5Merging (Combining)

Solution Approach 2:

The patent maintains continuous useful action by ensuring that as soon as the hydroformylation produces an aldehyde, it is immediately hydrogenated to alcohol, which is then immediately esterified. This continuous cascade eliminates idle time and intermediate isolation steps, maximizing the utilization of reaction time and improving overall process efficiency

Inventive Principle:

Principle #20Continuity of useful action

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 process efficiently converts olefins to esters with improved regioselectivity and avoids intermediate isolation, enhancing the production of esters with the desired carbon structure.

Implementation Method 1

Ru-catalysed domino hydroformylation/hydrogenation/esterification

Methodology Applied

Scientific EffectCatalysis: Catalysis

Implementation Method 2

domino hydroformylation/hydrogenation/esterification

Methodology Applied

Scientific EffectHydrogenation: Hydrogenation

Implementation Method 3

catalysed through the use of a ruthenium compound in combination with an acidic compound

Methodology Applied

Scientific EffectCatalysis: Catalysis

Data Source

PatentUS11773049B2Ru-catalyzed domino hydroformylation/hydrogenation/esterification using phosphine ligands

Publication Date: 2023.10.03 EVONIK OXENO GMBH & CO KG

AI summary

Ru-catalysed domino hydroformylation/hydrogenation/esterification using phosphine ligands.