Blue TiO2 Photocatalyst for Amide Synthesis from Tertiary Amines

Resolve Bottlenecks,
Find Innovative Solutions
Generate Solutions

Solution Overview

Problem

Current methods for synthesizing compounds with amide groups from tertiary amines require severe conditions and expensive metal catalysts, limiting their industrial applicability and environmental sustainability.

Innovation Solution

A method using reduced titanium dioxide (Blue TiO2) as a photocatalyst to synthesize amide groups from tertiary amines at room temperature, avoiding the need for expensive metal catalysts and severe conditions, by reacting tertiary amines with aldehydes under visible light irradiation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If conventional methods using expensive metal catalysts (palladium, ruthenium, iridium) are used to synthesize amide groups from tertiary amines, then the reaction can proceed, but the cost increases significantly and environmental sustainability deteriorates

Engineering Contradiction:
Improvereaction feasibilityVSAvoidcost-effectiveness
Core Design Contradiction:
ReliabilityVSEase of manufacture

Solution Approach 1:

The patent replaces expensive, precious metal catalysts (palladium, ruthenium, iridium) with a inexpensive semiconductor photocatalyst (titanium dioxide or zinc oxide). This substitution dramatically reduces material cost while maintaining catalytic functionality, directly resolving the contradiction between reaction feasibility and cost-effectiveness

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

Solution Approach 2:

The patent changes the operating parameters from thermal conditions (high temperature) to photochemical conditions (visible light irradiation). This parameter change enables the use of cheaper catalysts and reduces energy consumption, simultaneously improving cost-effectiveness while maintaining reliable amide bond formation

Inventive Principle:
Principle #35Parameter changes

2Reliability

If severe reaction conditions (high temperature) are applied to synthesize amide groups from tertiary amines, then the reaction proceeds, but energy consumption increases and environmental sustainability deteriorates

Engineering Contradiction:
Improvereaction efficiencyVSAvoidenergy consumption
Core Design Contradiction:
ReliabilityVSUse of energy by moving object

Solution Approach 1:

The patent substitutes thermal energy (heat) with optical energy (visible light) as the activation source. This replacement eliminates the need for high-temperature heating, dramatically reducing energy consumption while maintaining effective amide bond formation through photoexcitation of the semiconductor catalyst

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

Solution Approach 2:

The patent transitions from thermal reaction parameters (high temperature) to photochemical parameters (visible light irradiation, room temperature). This parameter change reduces energy input requirements while preserving reaction efficiency, resolving the contradiction between reliable amide synthesis and low energy consumption

Inventive Principle:
Principle #35Parameter changes

3Reliability

If conventional photocatalysts are used that require both anatase and rutile phases, then the photocatalytic activity is maintained, but the synthesis of amide groups from tertiary amines is not achieved

Engineering Contradiction:
Improvephotocatalytic activityVSAvoidsubstrate applicability
Core Design Contradiction:
ReliabilityVSAdaptability or versatility

Solution Approach 1:

The patent identifies that specific crystal phases (anatase or rutile alone) provide the necessary electronic structure and surface properties for activating tertiary amines. By optimizing for local quality in the crystal phase composition rather than requiring a specific mixture, the catalyst achieves both high photocatalytic activity and versatility with tertiary amine substrates

Inventive Principle:
Principle #3Local quality

4Temperature

If expensive metal catalysts are used for amide synthesis, then the reaction can proceed under mild conditions, but the method is not suitable for industrial application

Engineering Contradiction:
Improvereaction condition mildnessVSAvoidindustrial applicability
Core Design Contradiction:
TemperatureVSProductivity

Solution Approach 1:

The patent replaces expensive, scarce metal catalysts with abundant, inexpensive semiconductor materials. This substitution makes the process economically viable for industrial scale-up while maintaining mild reaction conditions, directly resolving the contradiction between mild operating conditions and industrial applicability

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

Solution Approach 2:

The patent develops a universal photocatalytic system using common semiconductors (TiO2, ZnO) that can process various tertiary amine substrates under visible light. This universality enables scalable industrial application while maintaining mild conditions, overcoming the limitation of expensive, specialized metal catalysts

Inventive Principle:
Principle #6Universality (Multi-functionality)

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 enables efficient and cost-effective synthesis of amide compounds at room temperature, using a single metal catalyst, and allows for repeated use of the photocatalyst, improving yield and reducing environmental impact.

Implementation Method 1

reacting a tertiary amine in the presence of the reduced titanium dioxide under visible light irradiation

Methodology Applied
Scientific EffectPhotocatalysis: Photo-oxidation

Implementation Method 2

by reacting tertiary amines with aldehydes under visible light irradiation

Methodology Applied
Scientific EffectLight absorption: Absorption (EM radiation)

Implementation Method 3

mixing a titanium dioxide (TiO2) having an anatase phase and a rutile phase with a reducing agent and selectively reducing any one of the anatase phase and the rutile phase

Methodology Applied
Scientific EffectSelective reduction: Reduction

Data Source

PatentUS12049436B2Preparing method of compounds including amide group from tertiary amine
Publication Date: 2024.07.30 RES & BUSINESS FOUND SUNGKYUNKWAN UNIV
  • US12049436B2 patent drawing
  • US12049436B2 patent drawing
  • US12049436B2 patent drawing

AI summary

Provided is a preparing method of an amide directly from a tertiary amine by using a reduced titanium dioxide (Blue TiO2), which is formed by mixing a titanium dioxide having an anatase phase and a rutile phase with a reducing agent and selectively reducing any one of the anatase phase and the rutile phase, as a photocatalyst.