Advancer Kilobatch. kilogram scale-up of all microwave chemistry

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Advancer Kilobatch kilogram scale-up of all microwave chemistry

Background MW reactions are become more common place in Discovery / Med Chem MW reactions can be higher yield / higher purity MW reactions are typically 10 to 1000 times faster MW can enable some chemistries that are impossible through traditional heating methods Many MW reactions (50-75%) are heterogeneous at either start, completion, or both MW difficulty at preclinical scale For delivery of first 100g and kgs, the smallest investment in re-optimization is best Time and Money spent for re-optimization will not bear fruit in large percentage of projects Fail early, fail cheaply No commercially available product that can scale all (or even most) chemistries to kg scale without a great deal of time (money) investment to tweak / optimize chemistry

Scale-up needs Speed fast & reproducible results Scalability no time for re-optimizations Support for all types of chemistry Safety

Choices Larger batch Make everything bigger Automated continuous batch Run many times at the same scale Flow through Perform the reaction in a continuous flow

Choices Larger batch Make everything bigger + no re-optimization adoptable to all chemistry quick turnaround - Safety concerns limited scale sufficient power stirring scalability?

Choices Automated continuous batch Run many times at the same scale + no re-optimization adoptable to all chemistry safe limitless scale sufficient power stirring - Turnaround time amendable for automation? reproducibility?

Choices Flow through Perform the reaction in a continuous flow + safe limitless scale - Turnaround time re-optimization required Not adoptable to all chemistry amendable for automation? reproducibility?

Choices Larger batch Make everything bigger Automated continuous batch Run many times at the same scale Flow through Perform the reaction in a continuous flow

Biotage Advancer 50-300 ml working volume Patent pending instant adiabatic cooling Mechanical stirrer Best-in-class safety Multiple vessel entry points Easy-to-use software 60-250 C operating temperature 1-20 Bar operating pressure range 1200 W power supply

Biotage Advancer 1L How do we get to: 1L total volume Any chemistry Heterogeneous Homogenous Unattended Direct scalability Maintaining the strengths

The Process Load Substrates, reagents and solvents React Power, stirring, temperature control etc Unload Undefined mixture

Pumping heterogeneous mixtures Heterogeneous flow in production Paper mills Petrochemicals Mining (Tailings) Food & brewages Large to enormous scale. Same process for up to 100+ years. Production economies of scale ptimization needed

Heterogeneous Flow Early Development Pharmaceuticals - heterogeneous flow for MAS New process every time No tuning time allowed Wide range of particle sizes large particles (small tubes) More than one solvent phase Very tight mixture requirements

ur solution Separate what cannot be mixed Wet-Wet (2 phases of liquid) Wet-Dry (pump + arm) Mix only when necessary Minimize transport of mixtures Avoid automated powder weighing

Advancer Kilobatch Hardware Solids Loading

Advancer Kilobatch Hardware Dry loading system 2 sizes of pocket catalyst ~ 500mg reagent ~ 90g K 2 C 3 4 sections (1 per cycle) Lid protects against drops Inert gas blanketing of reagents during standby

Advancer Kilobatch Hardware Dry loading performance 500 mg palladium on carbon, 1% loss 40 g magnesium sulphate 0,3-1,5% loss

Advancer Kilobatch Hardware Worst case dry loading: (sticky light powders) 500 mg ammonium acetate 0,2-6% loss (~2% per grain) 500mg Macroporous polystyrene 1,5% loss 15g Amberlyst ion exchanger 2,5% loss

Liquid loading Wet loading system Adjustable speed per solvent low tube losses: Priming N2 flushing Tested with DCM, Peg 400, Ammonia etc

Liquid loading Wet loading system Adjustable speed per solvent low tube losses: Priming N2 flushing Tested with DCM, Peg 400, Ammonia etc

React - Biotage Advancer 50-300 ml working volume 60-250 C operating temperature 1-20 Bar operating pressure range 1200 W power supply Mechanical stirrer Best-in-class safety Patent pending instant adiabatic cooling

Best-in class safety Best-in-class safety features 6 levels 1st level: Sash doors interlocks 2nd level: Software controlled safety loop 3rd level: Firmware controlled safety loop 4th level: Pre-calibrated pressure relief device on lid (30 bar) 5th level: Spring-loaded lid (35-55 bar) 6th level: Cavity bottom design( >66 bar) Breech lock

Unload Ejection system ne channel for reaction mixture ne channel to waste (cleaning cycles) Proven evacuation of slurries up to hard particles of 1-2mm Additional N2 flow available for ejection Adiabatic cooling Immediate cooling Decrease cycle time

Advancer Kilobatch Hardware verview 1 L total volume in 4 cycles (with solids) Removable vessels (solids cassette, RV, feed flasks, product vessel, etc) No extension of footprint Water cooled collection vessel Connection points for external collection vessel.

Advancer Kilobatch Software Preparation tab: Ensures system readiness Individual and system tests

Advancer Kilobatch Software Preparation tab: Ensures system readiness Individual and system tests

Advancer Kilobatch Software Manual Process tab For a single cup of product only

Advancer KiloBatch Software SBP Process Tab Sequential Cycles ptional Cleaning between cycles ptional cleaning after all cycles

Applications Prove use of homogenous reactions Prove use of hetrogenuous reactions Prove scalability Initiator -> Advancer Cycle to cycle Batch to batch Prove scale 10 s grams 100 s grams kg

Diels-Alder reaction; 50g Fully homogeneous; 50g: N + 1,2-DCE 160 C 10 min N Initiator: 94.0 % (conversion, by HPLC-MS at 210 nm) Addition of two stock solutions: 0.4 M in 1,2-DCE (125 ml, 1.0 equiv.) 0.6 M 1,3-Cyclohexadiene in 1,2-DCE (125 ml, 1.5 equiv.) Reaction also works nicely in flow chemistry

Diels-Alder N + 1,2-DCE 160 C 10 min N 0.4 M in 1,2-DCE (125 ml, 1.0 equiv.) 0.6 M 1,3-Cyclohexadiene in 1,2-DCE (125 ml, 1.5 equiv.) HPLC Purity 210 nm % 100 80 60 40 20 0 94 94,2 94,2 94,7 95,3 94,7 Initiator Batch 1 Cycle 1 13,0 g Batch 1 Cycle 2 13,4 g Batch 1 Cycle 3 13,4 g Batch 1 Cycle 4 13,5 g Batch 2 Cycle 1-4 53,2 g

Catalytic Transfer Hydrogenation; 30g Heterogeneous; 30g: N 10 % Pd/C Cyclohexene EtH 160 C 10 min N Initiator: 96.8 % (conversion, by HPLC-MS at 210 nm) 0.18 M Cyclohexene in EtH (250 ml, 1,5 equiv.) 0.96 g (3 % by mole) Pd/C as solid 8.02 g starting material as solid Did not work in flow due to solubility problems. Worked in DCE but with lower yield that got worse with time (catalyst poisoning)

Catalytic Transfer Hydrogenation N 10 % Pd/C Cyclohexene EtH 160 C 10 min N 0.18 M Cyclohexene in EtH (250 ml, 1,5 equiv.) 0.96 g (3 % by mole) Pd/C as solid 8.02 g starting material as solid HPLC Purity 210 nm % 100 80 60 40 20 0 96,8 94,1 94,2 94,6 94,8 94,1 Initiator Batch 1 Cycle 1 Batch 1 Cycle 2 Batch 1 Cycle 3 Batch 1 Cycle 4 Batch 2 Cycle 1-4 31,8 g

Alcohol-xidation; 120g Heterogeneous; 120g; repeated unload of solid materials: H Mn 2 1,2-DCE 200 C 20 min Initiator: 70.2 % (conversion, by HPLC-MS at 206 nm) Initiator EXP: 69.4 % 1.0 M in EtH (250 ml) 26.1 g (1.2 equiv.) Mn 2 as solid Remaining material is starting material

Mn 2 -xidation H Mn 2 1,2-DCE 200 C 20 min 1.0 M in EtH (250 ml) 26.1 g (1.2 equiv.) Mn 2 as solid HPLC Purity 206 nm 100 80 70,2 69,4 69,5 60 % 40 20 0 Initiator Initiator EXP Batch 1 Cycle 1-4

3-Component reaction; 40g Heterogeneous, Three additions; 40g; sensitive stoichiometry (1:1:1): N H NH 2 + + AcH DMF 220 C 15 min N H N Initiator: 77.6 % (conversion, by HPLC-MS at 236 nm) 0.283 M Benzylamine in DMF (125 ml) 0.283 M Benzaldehyde and Acetic acid in DMF (125 ml) 5.78 g Isatoic anhydride as solid Non-optimised for yield (can be optimized through stoichiometry)

3-Component reaction N H NH 2 + + AcH DMF 220 C 15 min N H N 0.283 M Benzylamine in DMF (125 ml) 0.283 M Benzaldehyde and Acetic acid in DMF (125 ml) 5.78 g Isatoic anhydride as solid HPLC Purity 236 nm 100 80 77,6 82,4 77,8 77,3 80,5 84,4 % 60 40 20 0 Initiator Batch 1 Cycle 1 Batch 1 Cycle 2 Batch 1 Cycle 3 Batch 1 Cycle 4 Batch 2 Cycle 1-4

Suzuki reaction, 45g Heterogeneous, four additions; 45g, premier MAS reaction; small additions: H N H Br N H + B H (Ph 3 P) 2 PdCl 2 Na 2 C 3.H 2 DME-H 2 -EtH (7:3:2) 160 C 10 min Initiator: 84.5 % (conversion, by HPLC-MS at 254 nm) 0.328 M Bromide in solution (125 ml) 0.492 M Boronic acid in DMF (125 ml) 0.360 g Catalyst as solid 7.63 g Na 2 C3.H 2

Suzuki reaction, heterogeneous N H + H B H (Ph 3 P) 2 PdCl 2 N H Br Na 2 C 3.H 2 DME-H 2 -EtH (7:3:2) 160 C 10 min HPLC Purity 254 nm 100 80 84,5 86 86,2 86,2 86,4 86,5 % 60 40 20 0 Initiator Batch 1 Cycle 1 Batch 1 Cycle 2 Batch 1 Cycle 3 Batch 1 Cycle 4 Batch 2 Cycle 1-4 70% after recrystallization; 81% after chromatography

Diels-Alder, 1240g Continuous homogeneous, 1240g, + DMF 160 C 10 min Initiator: 94.0 % (purity by HPLC-MS at 200 nm), 95 % (isolated yield) 1.0 M in DMF (7.0 L, 1.0 equiv.) 1.5 M in DMF (7.0 L, 1.5 equiv.) External reagent vessels External collection vessel Not restricted to four cycles

Continuous homogenous processing, 1.24 kg + DMF 160 C 10 min 1.0 M in DMF (7.0 dm 3, 1.0 equiv.) 1.5 M in DMF (7.0 dm 3, 1.5 equiv.) % 100 80 60 40 Purity and Yield 94 95 97,3 99 Data 56 runs 14.5 h 15.5 minutes/run 13.6 dm3 1.24kg isolated 20 0 Initiator purity Initiator yield Advancer purity Advancer yield

3-Component, heterogeneous, 600g Continuous heterogeneous, 604g, ClH H 2 N + + HS H DIEA EtH 160 C 10 min N S 0.879 kg 3,4,5-Trimethoxybenzaldehyde as solid (160 mmol, 2 eq) 0.314 kg Glycine ethyl ester x HCl as solid (80 mmol, 1 eq) 2.40 M Mercaptoacetic acid in EtH (2.80 L, 240 mmol, 3 eq) 1.00 M DIEA in EtH (2.80 L, 100mmol, 1.25 eq)

3-Component, heterogeneous, 600g ClH H 2 N + + HS H DIEA EtH 160 C 10 min N S 1.00 M DIEA in EtH (2.80 L) 0.314 kg Glycine ethyl ester x HCl as solid 2.40 M Mercaptoacetic acid in EtH (2.80 L) 0.879 kg 3,4,5-Trimethoxybenzaldehyde as solid % 100 80 60 40 20 0 60.8 Initiator conversion Conversion, Yield and Purity 66.8 Advancer KiloBatch conversion 79 76 Initiator yield Advancer KiloBatch yield 97.9 98.5 Initiator purity Advancer KiloBatch purity Data 28 runs 7 carousels 7 h 45 min 16 minutes/run ~1h/carousel 5.6 dm3 1.19 kg 0.60 kg isolated

Advancer Kilobatch- specification 60-250 C operating temperature 1-22 Bar operating pressure range (15 to 320 psi) 50-300 ml working volume per cycle 1L (with solids) to 24L runs without manual intervention Patent pending instant adiabatic cooling 1200 W power supply Multiple vessel entry points Mechanical stirrer Best-in-class safety Easy-to-use Software

Key Features & Benefits 1200W focused microwave device The powerful magnetron generates high energy fields that rapidly heats large volumes. Dynamic Field Tuning focuses the microwave energy to maximise the heating efficiency of every sample. Exact temperature and pressure measurement Ensures reaction control, reproducibility and safety Powerful stirring Ensures homogenity of heating and reproducibility of reactions with the use of heterogeneous reaction mixtures 300 ml batch mode processing The moderate scale-up factor ensures scalability and safety of temperature, high pressure reactions. Supports all chemistries. Sequential batch processing Separation of the phases gives reproducibility within and between runs, safely reacts smaller volumes while producing kgs of material Solid loading Patent pending Safe and accurate addition of insoluble materials. Inert blanketing ensures solid material quality. Results in high reproducibility and reliable automation of the process.

Key Features & Benefits Liquid loading Accurate dispensing of reagents ensures chemistry reproducibility Adiabatic flash evacuation/cooling Patent pending Gives efficient evacuation of the of homogenous and heterogeneuos reaction mixtures and enables reliable automation. Rapidly cools down the reaction temperature to below boiling point. Active cooling Makes sure the reaction stops after the evacuation Extra vessel entry points Can be used for addition of reagents, creating inert atmosphere or in-situ sampling when running single runs. Five-tier safety system The safest system on the market provides kilogram quantities with the same safety as lab-scale instruments Advancer Software Provides the same ease of use in the Advancer as in the Initiator instruments.

Summary Advancer Kilobatch provides fast and safe kilogram microwave scale-up of any chemistry; Homogeneous and heterogeneous. Enables chemists to quickly scale-up microwave chemistry without re-optimization Gives fast access to larger amounts of material to perform initial testing without loosing time 0.2-5 ml mg - g 20 ml 1-10 g 300 ml x 99 10 g - 1 kg