Adebar, Niklas: Towards Automation of Continuous Chemoenzymatic Syntheses of Plasticizers, Nitriles, and Chiral Esters from Renewable Resources. 2022
Inhalt
- Abstract
- Introduction
- Goals and Concept
- Synthesis of Novel Plasticizer Candidates
- Theoretical Background
- Concept
- Synthesis of Novel Plasticizers
- Plasticizer Performance Investigations
- Summary & Outlook
- Experimental
- Chemicals & Equipment
- Analytics
- Screening of the Synthesis of Racemic Bis(2-ethylhexyl) (1R*,2S*,3R*,4R*)-1-methyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (3) at 1 mL Scale
- Synthesis of Racemic Bis(2-ethylhexyl) (1R*,2S*,3R*,4R*)-1-methyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (3) at 30 g Scale
- Synthesis of Racemic Bis(2-ethylhexyl) (1R*,2S*,3R*,4R*)-1-methyl-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate (4) at 30 g Scale
- Synthesis and Purification of Racemic Bis(2-ethylhexyl) (1R*,2S*,3R*,4R*)-1-methyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (3) at 300 g Scale
- Synthesis of Racemic Bis(2-ethylhexyl) (1R*,2S*,3R*,4R*)-1-methyl-7-oxabicyclo[2.2.1]heptane-2,3-dicarboxylate (4) at 300 g Scale
- Synthesis of Racemic Bis(2-ethylhexyl) (1R*,2S*,3S*,4R*)-1-methyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (6)
- Praparation of Er(OTf)3 SILP
- Synthesis of Racemic Bis(2-ethylhexyl) (1R*,2S*,3R*,4R*)-1-methyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (3) using Er(OTf)3 SILP
- Continuous Synthesis of Racemic Bis(2-ethylhexyl) (1R*,2S*,3R*,4R*)-1-methyl-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (3) using Er(OTf)3 SILP
- Performance Tests of Plasticizer 4
- Closed-loop Optimization Platform
- Theoretical Background
- Concept
- Software Modules
- Closed-loop Optimization Platform
- Hardware Modules
- Summary & Outlook
- Chemoenzymatic Continuous Nitrile Synthesis
- Theoretical Background
- Concept
- Synthesis of Alkyl Nitriles from Renewables
- Summary & Outlook
- Experimental
- Analytics
- Chemicals & Equipment
- Preparation of OxdB from Bacillus sp. OxB-1 Whole Cells
- TEMPO-catalyzed Oxidation of 1-Octanol (12)
- Validation of the Quenching Method
- Synthesis of Octanal (13) in DCM Batch
- Synthesis of Octanal (13) in Aqueous/DCM Batch
- Synthesis of Octanal (13) in Aqueous/DCM Segmented Flow
- Synthesis of Octanal oxime (14)
- Synthesis of Octanal oxime (14) in Segmented Flow
- Algorithm-assisted Optimization of the Synthesis of Octanal oxime in Segmented Flow
- Closed-loop Optimization of the Synthesis of Octanal oxime (14) in Segmented Flow
- Whole-cell Catalysis in Segmented Flow
- Synthesis of Octanenitrile (15) in Buffer/cyclohexane Batch Mode
- Synthesis of Octanenitrile (15) in Buffer/cyclohexane 10 mL Scale Batch Mode
- Synthesis of Octanenitrile (15) in Buffer/cyclohexane Segmented Flow
- Fluid Heterogeneous Catalysis in Segmented Flow
- Chemoenzymatic Continuous Flow Dynamic Kinetic Resolution
- Theoretical Background
- Towards Continuous Flow Dynamic Kinetic Resolution
- Lipase-catalyzed Acylation
- Vanadium-catalyzed Racemization of Chiral Alcohols
- Dynamic Kinetic Resolution
- Summary
- Experimental
- General Working Conditions
- Chemicals & Equipment
- Analytics
- Synthesis of (rac)-(E)-4-(4-Methoxypehnyl)but-3-en-2-ol (18)
- Synthesis of (rac)-(E)-4-(4-Methoxypehnyl)but-3-en-2-yl acetate (19)
- Kinetic Resolution of Alcohol 18 in Flow
- Racemization of Alcohol 18 in Flow
- DKR of Alcohol 18 in Flow
- DKR of Alcohol 18 in Flow with a Gradient Packed Bed Reactor
- References