Dehalogenation of trans-1233zd to TFP

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Solution Overview

Problem

Current methods for producing 3,3,3-trifluoropropyne (TFP) are expensive and inefficient due to the use of costly and hazardous reactants, and the trans-1-chloro-3,3,3-trifluoropropene isomer is thermodynamically favored, resulting in low yields and environmental concerns.

Innovation Solution

Contacting trans-1-chloro-3,3,3-trifluoropropene with a potassium-containing base, such as potassium hydroxide or potassium tert-butoxide, to produce TFP at a higher yield, using commercially available and recyclable solvents like tert-butanol and ether, with preferred molar ratios to minimize side reactions.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If conventional methods (LDA or MeLi at -80°C) are used to deprotonate trans-1233zd, then TFP lithium salt can be obtained, but the process becomes expensive and requires specialized reagents

Engineering Contradiction:
ImproveTFP production yieldVSAvoidManufacturing cost
Core Design Contradiction:
Quantity of substanceVSEase of manufacture

Solution Approach 1:

The patent replaces expensive, specialized reagents (LDA, MeLi) with cheaper, more stable potassium-containing bases (KOH, KOtBu) that can be obtained commercially and are less hazardous, thereby reducing manufacturing cost while maintaining TFP production capability

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

Solution Approach 2:

The patent changes the base used from organolithium/organometallic compounds to potassium hydroxide or potassium tert-butoxide, fundamentally altering the reagent type from strong organometallic base to inorganic/alkoxide base, which improves ease of manufacture while maintaining effectiveness

Inventive Principle:
Principle #35Parameter changes

2Quantity of substance

If sodium amide is used as base for dehydrochlorination of trans-1233zd, then TFP can be produced, but the process becomes expensive and hazardous due to toxicity and hazardous nature of reactants

Engineering Contradiction:
ImproveTFP production yieldVSAvoidToxicity and hazardous nature of reactants
Core Design Contradiction:
Quantity of substanceVSObject-affected harmful factors

Solution Approach 1:

The patent replaces toxic and hazardous sodium amide with safer, less hazardous potassium-containing bases (KOH, KOtBu) that are commercially available and environmentally friendlier, thereby reducing harmful factors while maintaining TFP production capability

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

Solution Approach 2:

The patent converts the previously harmful and hazardous reaction conditions into safer, more environmentally friendly conditions by using potassium-based bases that are less toxic and more stable, turning a hazardous process into a safer one

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

3Quantity of substance

If zinc is used in DMF at 100°C for dehydrochlorination, then TFP can be produced with 75% yield, but environmentally related expenses arise and the process requires multiple steps

Engineering Contradiction:
ImproveTFP production yieldVSAvoidEnvironmental impact
Core Design Contradiction:
Quantity of substanceVSObject-affected harmful factors

Solution Approach 1:

The patent replaces zinc (which causes environmental problems) with potassium-containing bases that are environmentally friendlier and can be used under milder conditions, thereby reducing environmental impact while maintaining good yield

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

Solution Approach 2:

The patent changes the reaction conditions from high temperature (100°C) and zinc-mediated to lower temperature potassium base-mediated dehydrochlorination, improving environmental compatibility while maintaining efficiency

Inventive Principle:
Principle #35Parameter changes

4Quantity of substance

If trans-1233zd is used as feedstock, then TFP can be produced, but the cis isomer is thermodynamically favored and only 3-5% cis isomer is formed in conventional processes

Engineering Contradiction:
ImproveTFP production yieldVSAvoidIsomer composition
Core Design Contradiction:
Quantity of substanceVSStability of the object's composition

Solution Approach 1:

The patent changes the base used in the deprotonation reaction, which alters the reaction pathway and thermodynamic landscape, enabling better control over isomer formation and improving the stability of the desired cis isomer composition

Inventive Principle:
Principle #35Parameter changes

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 allows for the safe and economical production of TFP on a commercial scale with yields ranging from 16.3% to 29.0%, utilizing non-toxic and environmentally friendly reactants, reducing operational costs and environmental impact.

Implementation Method 1

trans-1-chloro-3,3,3-trifluoropropene is treated with a potassium-containing base, e.g., potassium hydroxide or potassium tert-butoxide, to produce TFP

Methodology Applied
Scientific EffectDehydrochlorination:

Data Source

PatentUS9216932B2Dehalogenation of trans-1-chloro-3,3,3-trifluoropropene
Publication Date: 2015.12.22 SOLSTICE ADVANCED MATERIALS US INC

AI summary

The present invention is related to making hydrofluorocarbons (HCFCs), more specifically, 3,3,3-trifluoropropyne (TFP), from trans-1-chloro-3,3,3-trifluoropropene (trans-1233zd) by contacting the trans-1233zd with a base. Preferably, the base is potassium hydroxide or potassium tert-butoxide, which may or may not be dissolved in as solvent.