Methoxyborane Synthesis via Formic Acid Disproportionation

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Solution Overview

Problem

Current methods for producing methanol from CO2, such as hydrogenation and electro-reduction, face challenges like low selectivity, high energy requirements, and the use of expensive and toxic noble metals, while disproportionation of formic acid is limited to metal-based catalysts with low selectivity and efficiency.

Innovation Solution

A process involving the disproportionation of formic acid or its derivatives in the presence of organoboranes to form methoxyboranes, which are then hydrolyzed or protonolyzed to produce methanol, using a metal-free approach with organoboranes as catalysts, avoiding the limitations of traditional metal-based systems.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Ease of manufacture

If hydrogenation or electro-reduction of CO2 is used to produce methanol, then methanol can be produced from renewable sources, but the selectivity is low and expensive noble metal catalysts are required

Engineering Contradiction:
Improvemethanol production from renewable sourcesVSAvoidselectivity
Core Design Contradiction:
Ease of manufactureVSManufacturing precision

Solution Approach 1:

The patent changes the chemical parameters by using formic acid derivatives (methyl formate, formates) as intermediates instead of direct CO2 reduction, and employs organoborane catalysts with specific structural parameters (R1, R2 groups) to achieve high selectivity for methoxyborane formation, which then hydrolyzes to methanol with >90% selectivity

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent replaces expensive noble metal catalysts (Ru, Ir) with inexpensive organoborane compounds that can be used in catalytic amounts and regenerated through hydrolysis of methoxyborane intermediates, reducing catalyst cost while maintaining high efficiency

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

2Productivity

If hydrogenation of CO2 is used to produce methanol, then methanol can be produced, but high pressure and temperature conditions are required

Engineering Contradiction:
Improvemethanol productionVSAvoidenergy requirements
Core Design Contradiction:
ProductivityVSUse of energy by moving object

Solution Approach 1:

The patent performs preliminary conversion of CO2 to formic acid or its derivatives (methyl formate, formates) through low-energy 2-electron reduction or esterification, then uses these stabilized intermediates in the disproportionation reaction with organoboranes under mild conditions (room temperature to 60°C, atmospheric pressure), avoiding the high energy input required for direct CO2 hydrogenation

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The patent segments the overall methanol synthesis from CO2 into two distinct stages: (1) formation of formic acid derivatives through low-energy processes, and (2) disproportionation of these derivatives with organoboranes to form methoxyboranes, which are then hydrolyzed to methanol. This segmentation allows each stage to operate under optimized, lower-energy conditions

Inventive Principle:
Principle #1Segmentation

3Productivity

If metal-based catalysts are used for disproportionation of formic acid, then the reaction can proceed, but selectivity and efficiency are low

Engineering Contradiction:
Improvedisproportionation reaction rateVSAvoidselectivity
Core Design Contradiction:
ProductivityVSManufacturing precision

Solution Approach 1:

The patent replaces traditional metal-based catalysts with organoborane compounds (RBH2, R2BH, R3B) that are inexpensive, non-toxic, and can be used in catalytic amounts. The organoboranes form methoxyborane intermediates that hydrolyze to release methanol and regenerate the organoborane catalyst, achieving both high productivity and selectivity without metal contamination

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent employs organoborane molecules with specific composite structures (combining boron center with organic R groups like alkyl, aryl, or heteroaryl substituents) to create catalysts that combine the reactivity of boron with the stability and tunability of organic moieties, achieving high selectivity and efficiency in the disproportionation reaction

Inventive Principle:
Principle #40Composite materials

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 offers a more efficient and selective production of methanol with reduced costs and toxicity, utilizing readily available and inexpensive organoboranes, and allows for the reuse of generated gases and catalysts, enhancing the economic viability and environmental impact of methanol production.

Implementation Method 1

disproportionation of formic acid or at least one of its derivatives or of a mixture of formic acid and at least one of its derivatives, in the presence of an organoborane

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

a step of hydrolyzing or protonolyzing the methoxyborane into methanol

Methodology Applied
Scientific EffectHydrolysis: Hydrolysis

Data Source

PatentEP3374363B1Method for preparing methoxyboranes and for producing methanol
Publication Date: 2020.04.01 COMMISSARIAT A LENERGIE ATOMIQUE ET AUX ENERGIES ALTERNATIVES
  • EP3374363B1 patent drawingFigure 1~3
  • EP3374363B1 patent drawingFigure 4~6
  • EP3374363B1 patent drawingFigure 7

AI summary

The present invention relates to a method for preparing methoxyboranes by dismutation of the formic acid or at least one of the derivatives thereof or a mixture of formic acid and at least one of the derivatives thereof, in the presence of an organoborane, and optionally an organic or inorganic base. The invention also relates to a method for producing methanol which includes a step of preparing a methoxyborane according to the method of the invention and a step of hydrolysis or protonolysis of the methoxyborane into methanol. The invention furthermore relates to the use of methoxyboranes obtained by the method of the invention for the production of methanol, as catalysts in allylation reactions, as reagents in Suzuki coupling reactions, and as a reagent for fine chemistry or for heavy chemistry. The methanol produced by hydrolysis or protonolysis of the methoxyboranes formed by the method of the invention can be used as a fuel or additive in combustion engines, as a fuel in direct methanol fuel cells, as a means for storing hydrogen, or as a reagent for fine chemistry.