Macrocyclic Diketone Synthesis via Ruthenium Catalysis
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Solution Overview
Problem
Current processes for producing macrocyclic diketone compounds, such as cyclopentadecane-1,5-dione and 3-methylcyclopentadecane-1,5-dione, face challenges on industrial scales due to the use of hazardous, expensive, or difficult-to-handle reagents, including ozone, singlet oxygen, potassium permanganate, and sodium periodate, which complicate large-scale production and generate toxic waste.
Innovation Solution
A process utilizing a catalytic amount of a ruthenium compound as the oxidizing agent in combination with oxyanions of chlorine as a co-oxidizing agent for the oxidation of bicycloolefine compounds, allowing for efficient conversion to diketone compounds with good yields and selectivity, avoiding the use of hazardous reagents and enabling easier handling and recycling of ruthenium compounds.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Productivity
If ozone or singlet oxygen is used for oxidation, then macrocyclic diketones can be produced, but the process becomes difficult to handle on large scale
Solution Approach 1:
The patent changes the chemical parameters of the oxidation system by replacing gaseous ozone or photochemically generated singlet oxygen with a catalytic ruthenium system using conventional oxidants (sodium hypochlorite, hydrogen peroxide, or oxygen). This parameter change transforms the oxidation process from one requiring specialized equipment and safety measures to a readily scalable industrial process using standard chemical reagents.
2Productivity
If potassium permanganate is used for oxidation, then macrocyclic diketones can be produced, but the work-up procedure becomes difficult and laborious
Solution Approach 1:
The patent extracts the problematic work-up steps associated with potassium permanganate by replacing it with a ruthenium-catalyzed oxidation system. The ruthenium catalyst can be easily removed by filtration, and the reaction mixture requires minimal work-up compared to permanganate oxidations, which generate manganese dioxide precipitates requiring extensive filtration and purification.
3Productivity
If sodium periodate is used for oxidation, then macrocyclic diketones can be produced, but the reagent becomes expensive and requires high technical safety requirements
Solution Approach 1:
The patent replaces expensive sodium periodate with cheaper, readily available oxidants such as sodium hypochlorite (bleach), hydrogen peroxide, or molecular oxygen. These reagents are significantly less expensive, have lower safety requirements, and can be handled using standard industrial equipment without special safety infrastructure.
4Productivity
If stoichiometric amounts of oxidizing agents are used, then oxidation can be achieved, but the process becomes expensive and generates toxic waste
Solution Approach 1:
The patent implements catalyst recovery by filtering the reaction mixture to remove the ruthenium catalyst, which can then be reused in subsequent reactions. This recovery approach eliminates the need for stoichiometric amounts of expensive oxidants and reduces waste generation, as the catalytic system can be regenerated and reused multiple times.
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 approach enables the production of macrocyclic diketones on an industrial scale with high yields and selectivity, reducing the need for expensive and hazardous reagents, simplifying the process, and minimizing waste generation, thus overcoming the limitations of previous methods.
Implementation Method 1
utilizing a catalytic amount of a ruthenium compound as the oxidizing agent
Implementation Method 2
oxidation of a bicycloolefine compound of the formula (II) with an oxidizing agent
Implementation Method 3
co-oxidizing agent selected from oxyanions of chlorine
Data Source
AI summary
The present invention relates to a process for preparing a macrocyclic diketone compound of the formula (I), which comprises the oxidation of a bicycloolefine compound of the formula (II) with an oxidizing agent, formulae (I) (II) where in formulae (I) and (II) A is (CH2)n with n being an integer from 2 to 12, where two hydrogen atoms may be replaced by C1-C4-alkyl, in particular methyl, or two hydrogen atoms, which are bound to adjacent carbon atoms may be replaced by a fused 5- or 6-membered saturated carbocycle; B is (CH2)m with m being 1 or 2, where 1 or 2 hydrogen atoms may be replaced by C1-C4-alkyl, in particular methyl.