application note - silicyclelanthanides are widely used in organic synthesis and for a wide range of...

NSi P

PHO

HO

OH

OH

O

OMetal Scavenging

with SiliaMetS® AMPA

Application Note :

SiliaMetS AMPA PN : R85130BScavenger Name : Si-Aminopropyl-N1N-Bis (methyl phosphonic acid) ; Si-AMPA ; ((propylazanediyl)bis(methylene))diphosphonic acid grafted silica

Chemical Formula : Si-C5H12NO6P2

Description : Metal Scavenger

Particle Size*: 40 - 63 µm

Pore Diameter*: 60 Å

Surface Area : 480 - 550 m2/g

Pore Volume : 0.70 - 0.85 g/mL

Molecular Loading : ≥ 0.80 mmol/g

Typical Tap Density : 707 g/L

Appearance : Yellow

Solvent Compatibility : All solvents, organic and aqueous

Prolonged Storage : Keep dry

Shelf-Life : 1 year

AbstractEffectively eliminates Iron, Copper, Zinc, Manganese, Lanthanides, Antimony and Nickel.

SiliaMetS AMPA is a silica-supported Aminomethylalkylphosphonic acid ligand.

It is our best scavenger for the scavenging of Antimony (Sb), Nickel (Ni), Manganese (Mn), Lanthanides (La) and Vanadium (V). It is especially strong for the chelating of Cerium (Ce).

*Other silica matrices available on request

NH2 P OH

OH

O

HON

N

OH

OH

O OH

O

O

O

Hydrogen Helium

Lithium Beryllium Boron Carbon Nitrogen Oxygen Fluorine Neon

Sodium Magnesium Aluminum Silicon Phosphorus Sulfur Chlorine Argon

Potassium Calcium Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton

Rubidium Strontium Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon

Cesium Barium Lanthanides

Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium

Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury Thallium Lead Bismuth Polonium Astatine Radon

Francium Radium Actinides

Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium

Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium

*Lanthanides

**Actinides

1 (IA) 18 (VIIIA)

2 (IIA)

-259.14-252.87

2.2-1,1

H1.00791

0.089

3 (IIIB) 4 (IVB) 5 (VB) 6 (VIB) 7 (VIIB) 8 (VIII) 9 (VIII) 10 (VIII) 11 (IB) 12 (IIB)

13 (IIIA) 14 (IVA) 15 (VA) 16 (VIA) 17 (VIIA)

180.541347

1.01

Li6.9413

0.534

97.81882.9

1.01

Na22.99011

0.971

63.357740.9

1

K39.09819

0.86

12782970

1.52

Be9.01224

1.85

648.81090

1.22

Mg24.30512

1.738

8391484

1.02

Ca40.07820

1.55

38.896880.9

1

Rb85.46837

1.532

28.40678.4

0.91

Cs

Fr

132.9155

1.873

276770.9

1

223.0287

7691384

1.02

Sr87.6238

2.54

7251640

1.02

Ba137.3356

3.5

7001140

1.02

Ra226.0388

5.0

15412831

1.23

Sc44.95621

2.99

15223338

1.13

Y88.90639

4.47

**89-103

16603287

1.33,4

Ti47.8822

4.54

18524377

1.24

Zr91.22440

6.51

22274602

1.24

Hf178.4972

13.3

Rf261.11104

18903380

1.52,3,4,5

V50.94223

6.11

24684742

1.23,5

Nb92.90641

8.57

29965425

1.35

Ta180.9573

16.6

18572672

1.62,3,6

Cr51.99624

7.19

26174612

1.32,3,4,5,6

Mo95.9442

10.2

34105660

1.42,3,4,5,6

W183.8474

19.3

7993426

1.13,4

Ce140.1258

6.66

9313512

1.13,4

Pr140.9159

6.77

10213068

1.13

Nd144.2460

7.00

11682460

1.13

Pm146.9261

7.26

17504790

1.14

Th232.0490

11.7

1600

1.14,5

Pa231.0491

15.4

11323818

1.23,4,5,6

U238.0392

19.0

6403902

1.23,4,5,6

Np237.0593

20.2

6413232

1.23,4,5,6

Pu244.0694

19.8

10771791

1.12,3

Sm150.3662

7.52

31805627

1.52,4,7

186.2175

21.0

8221597

1.02,3

Eu151.9663

5.24

9942607

1.23,4,5,6

A m243.0695

13.7

21724877

1.47

Tc

Re

98.90643

11.5

12441962

1.62,3,4,6,7

Mn54.93825

7.43

15352750

1.62,3,6

Fe55.84526

7.86

23103900

1.43,4,8

Ru101.0744

12.4

30455027

1.52,3,4,6,8

Os190.2376

22.6

14952870

1.62,3

Co58.93327

8.9

19663697

1.51,2,3,4

Rh102.9145

12.4

24304430

1.61,2,3,4,6

Ir192.2277

22.4

13133266

1.13

Gd157.2564

7.90

1340

1.23,4

Cm247.0796

13.51.23,4

Bk247.0797

141.23,4

Cf251.0898

1.23

Es252.0899

1.23

Fm257.18100

1.23

Md258.01101

2,3

No259.10102

3

Lr262.11103

13563123

1.13,4

Tb158.9365

8.23

14122562

1.13

Dy162.5066

8.55

14742695

1.13

Ho164.9367

8.80

14972900

1.13

Er167.2668

9.07

15451947

1.12,3

Tm168.9369

9.32

8191094

1.12,3

Yb173.0470

6.97

16633395

1.13

Lu174.9771

9.84

14532732

1.82,3

Ni58.69328

8.90

10832567

1.81,2

Cu63.54629

8.96

419.69071.7

2

Zn65.3930

7.13

15523140

1.42,4

Pd106.4246

12.0

10642807

1.41,3

Au196.9779

19.3

17723827

1.42,4

Pt195.0878

21.4

961.92212

1.41,2

Ag107.8747

10.5

320.97651.5

2

Cd112.4148

8.65

-38.841356.6

1.51,2

Hg200.5980

13.5

303.51457

1.41,3

Tl204.3881

11.85

271.31560

1.73,5

Bi208.9883

9.75

2549621.8

2,4,6

Po209.9884

9.32

3023372.0

-1,1,3,5,7

At209.9985

11.3

-71-61.8Rn

222.0286

9.73

156.52080

1.53

In114.8249

7.31

232.02270

1.72,4

Sn118.7150

7.31

29.782403

1.83

Ga69.72331

5.904

630.71750

1.8-3,3,5

Sb121.7651

6.69

937.42830

2.04

Ge72.6132

5.32

449.59902.0

-2,4,6

Te127.6052

6.24

660.372467

1.53

Al26.98213

2.699

20792550

2.03

B10.8115

2.34

33674827

2.5-4,2,4

C12.0116

2.25

14102355

1.74

Si28.08614

2.33

113.5184.4

2.2-1,1,3,5,7

I126.9053

4.93

-111.9-107.1Xe

131.2954

5.85

8176132.2

-3,3,5

As74.92233

5.73

217684.9

2.5-2,4,6

Se78.9634

4.79

-7.258.78

2.7-1,1,3,5,7

Br79.90435

3.12

-156.6-152.3Kr83.8036

3.71

44.12802.1

-3,3,5

P30.97415

1.82

-209.86-195.8

3.1-3,2,3,4,5

N14.0077

1.25

-218.4-182.96

3.5-2,-1

O15.9998

1.43

112.8444.67

2.4-2,2,4,6

S32.06616

2.07

-219.62-188.14

4.1-1

F18.9989

1.69

-100.98-34.6

2.8-1,1,3,5,7

Cl35.45317

3.21

<-272.2-268.93He

4.00262

0.17

-248.67-246.05Ne20.1810

0.90

-189.2-185.7Ar

39.94818

1.78

Db262.11105

Sg266.12106

Bh264.12107

Hs269.13108

Mt268.14109

Ds271.15110

Rg272.15111

Cn285112

9213457

1.13

La138.9157

6.145

Lanthanum

*57-71

10503200

1.03

Ac227.0389

10.1

Actinium

Ununquadium

Uuq289114

Ununhexium

Uuh289116

Ununoctium

Uuo293118

Ununtrium Ununpentium Ununseptium

Uus293117

Uup291115

Uuo287113

327.51740

1.62,4

207.282

11.4

Pb

Best scavenger

Good scavenger

SiliCycle Application Noteswww.SiliCycle.com | [email protected]

Description • Scavengers are our class of functionalized silica that exhibit

ability to bond (that is, to “scavenge”) various metal compounds or organic molecules dissolved in solution.

• Recently, the need to carry out more challenging coupling reactions has resulted in the development of more advanced catalysts and the use of many different metals.

• Hence, more and more sophisticated scavengers are needed, with improved chelating properties for more than just standard transition metals (Pd, Pt, etc.).

• SiliaMetS AMPA is a silica-supported aminoalkylphosphonic acid ligand : it has an aminopropyl linker and two (2) methylphosphonic acid functional groups.

• It is a function known for its good metal chelating abilities.

• SiliaMetS AMPA is the first AMPA silica-supported on the market and a very powerful tool to scavenge Lanthanides, but it is also very potent for metals such as Aluminium, Antimony, Cobalt, Copper, Iron, Manganese, Nickel, Vanadium, and Zinc.

• Its chemical structure is reminiscent of EDTA (Scheme 1).

Typical Applications and UsesTypical applications include – but not limited to – the following reactions and/or the following catalysts scavenging (Table 1)

Reactions / Catalysts Metal / Catalyst to be scavenged

Pudovik reaction LaCl3

Biginelli pyrimidone synthesis LaCl3 or CoCl3

Binol catalyst La-BINOL

Fischer indole synthesis Zn

Friedel-crafts acylation Zn

Lactonisations Mn

Mannich-type reactions Zn, La

Table 1 : Scavenging activity for metals by SiliaMetS AMPA

Si-AMPA is not suitable and should not be used for precious metals (Ru, Rh, Pd & Pt). SiliCycle developed scavengers especially for these metals with stronger chelating compatibilities : Si-Cysteine, Si-DMT, Si-TAAcONa, Si-Thiol, Si-Thiourea (please refer to our scavenger portfolio p. 6).

Lanthanides are widely used in organic synthesis and for a wide range of biological, medicinal and synthetic applications, such as metallurgical applications, oil refining industry, ceramics etc. They have been used to impart strength, hardness, and inertness to structural materials. Furthermore, they are known to remove oxygen and sulphur impurities from systems.

Our SiliaMetS AMPA is the first silica-supported AMPA on the market, and it is produced in large scale at our state-of-the-art facilities.

AMPA

EDTA

Scheme 1

This screening, as well as the reactions in our case studies were all successfully conducted using SiliCycle MiniBlock®, a unique and powerful tool designed for parallel synthesis, quick screenings and optimization studies.

3

Preliminary ScreeningMetal complex solutions were solubilized in dimethylformamide (DMF) and shaken with four (4) molar equivalents of SiliaMetS AMPA at room temperature (22°C). Residual concentrations of metals were measured by ICP-OES.

Complex MetalScavenging efficiency in %

4 h at 22°C 8 h at 22°C 16 h at 22°C

Cu(OTf)2 Cu 64 86 94

Ca(OTf)2 Ca 78 51 67

LaCl3 La 61 91 65

Zn(OAc)2 Zn >99 >99 >99

FeCl3 Fe 79 98 77

CeCl3 Ce 80 95 84

Mn(OAc)2 Mn >99 >99 >99

Al(NO3)3 Al 70 91 83

Grubb1s Ru 17 - -

RhCl(PPh3)3 Rh 11 - -

Pd(PPn3)4 Pd 41 49 -

H2PtCl6 Pt 39 - -

Table 2 : SiliaMetS AMPA scavenging efficiency (%) toward various metal complexes.

Note : Scavenging were performed in DMF, using 4 molar equivalents.

As stated in Table 2, SiliaMetS AMPA was tested with several metallic complexes in DMF. Ce, La, Zn, Fe, Cu, Mn and Al were well retained by the scavenger, as precious metal (Ru, Rh, Pd and Pt) were poorly chelated.

Typical Experimental Procedures in Batch Reactor Mode (Bulk)For initial screening, start with 4 - 8 molar equivalents of SiliaMetS in respect to the residual metal concentration

1.Dissolve the crude product to be treated in a suitable solvent (or use directly the crude reaction mixture) and prepare vials containing the same solution volume.

2. Directly add your chosen SiliaMetS to these vials.1

3. For initial tests, stir the solution for at least one hour at room temperature.

4.

Scavenging progress can be followed by normal analytical techniques.

The scavenging progress can also be estimated by looking the color of the solution, as demonstrated in the picture below.

When the scavenging is almost complete, the solution is generally less colored and SiliaMetS becomes colored itself. In some occasional cases, if all the samples are still colored, try one or all of the following : let them react for a longer period of time ; add more equivalents of the SiliaMetS, increase the temperature of the reaction. Keep in mind that colors can come from other factors unrelated to the impurities.

5. At the end of the scavenging, filter off the SiliaMetS using a fritted funnel or filtration device.

6.Wash the SiliaMetS with additional solvent for total recovery of the API (or compound of interest) and concentrate the solution under vacuum.

7.Analyze the residual metal concentration of each vial to identify the most efficient SiliaMetS Metal Scavenger. (More than one can be chosen.)

8. Direct scale-up is possible. Otherwise, scavenging optimization can be examined

1 Note : no pre - wetting of the SiliaMetS is required.

Please keep in mind that the above procedures are standard and introductory, and that optimization of conditions is key to optimal results.

Figure 1. Graph represents residual concentration (%) of Pd(OAc)2 with SiliaMetS Thiol in DMF.

Figure 3

Figure 2


Experiment Optimization If, upon completion of the screening procedure, the scavenging is not complete or you wish to either reduce the number of equivalents or the reaction time, optimization steps can be undertaken.Various parameters can be changed one at a time or simultaneously to improve the metal removal efficiency.Note : you can mix multiple scavengers to get superior efficiency.

Number of SiliaMetS or SiliaBond EquivalentsFor initial screening experiments we suggest 4 - 8 molar equivalents for SiliaMetS and 2 - 4 molar equivalents for SiliaBond be used in respect to the residual impurities concentration of each scavengers. Once the preferred scavenger is identified, further optimization can be done to reduce the number of equivalents used (typically down to 2 - 4 equivalents).

Subsequent Treatments with SiliaMetS or SiliaBondIn some cases (equilibrium process or the presence of multiple species), multiple treatments with our scavengers is suitable instead of a single treatment with a larger amount.For optimal results, filtration between each treatment can allow for a higher scavenging efficiency.

TemperatureIn initial screening, we suggest the scavenging experiments be run at room temperature. Usually, scavenging is completed after one hour to four hours. However, when shorter scavenging times are required, higher scavenging rates can be achieved by increasing the temperature. SiliaMetS and SiliaBond can be safely used at elevated temperature without degradation and can be added either at room temperature or directly to a warm solution.

SolventSiliaMetS and SiliaBond can safely be used in a wide range of organic and aqueous solvents commonly used in laboratory and in process, such as DMF, DMSO, THF, 2-butanone, alcohols, ethers, chlorinated solvent, etc. As demonstrated in figures 2 and 3, the nature of the solvent does sometimes influence scavenging efficiency. If scavenging or kinetics are too slow, changing solvent or adding a co-solvent should be considered.

Mixing RateOur scavengers are mechanically stable and offer excellent scavenging efficiency in batch processes agitated by overhead stirrers as well as orbital shaking under low to moderate agitation rates.If required, mixing rates can be increased to get better scavenging results. With faster stirring, you improve the scavenger dispersion in solution.

Reaction TimeIn some cases, where increasing the temperature is impossible, longer contact time with the scavenger can allow higher scavenging efficiency.

pH of the Aqueous SolutionWhen the scavenging is done in aqueous solutions, it is possible to use our scavengers in a pH range of 2 to 12. Depending on the nature of the scavenging agent, pH can modify the functional groups present on the scavengers by charging them. Scavenging can be affected (i.e, amine groups in acidic conditions).

SiliaMetS or SiliaBond Format (Mode Used)One advantage of our scavengers is their compatibility with various technologies. They can be used in batch, in fixed bed (SPE or Flash cartridges), in flow chemistry, or in microwave. Scavenging efficiency can be improved by changing the mode used.

5

Ordering Information

SiliaMetS AMPA Bulk Ordering Information

PN Formats

R85130B 5 g, 10 g, 25 g, 50 g, 100 g, 250 g, 500 g, 1k g, 5 kg, 10 kg, 25 kg, …up to multi - ton scale.

SiliaMetS AMPA is Also Available in Fixed Bed Mode (SPE or Flash Cartridges)

SiliaSep™ AMPA Flash Cartridges Ordering Information

PN Sorbent weight Qty / box PN Sorbent weight Qty / box

FLH-R85130B-ISO04 4 g 2 FLH-R85130B-IS120 120 g 1




FLH-R85130B-ISO80 80 g 1 FLH-R85130B-I1500 1600 g 1

SiliaSep™ OT (Open Top) AMPA Cartridges Ordering Information

PN Sorbent weight Volume Qty / box PN Sorbent weight Volume Qty / box

FLH-R85130B-15U 2 g 12 mL 20 FLH-R85130B-95K 25 g 150 mL 10

FLH-R85130B-70Y 10 g 70 mL 16 FLH-R85130B-95M 50 g 150 mL 10

FLH-R85130B-70i 15 g 70 mL 16 FLH-R85130B-95N 70 g 150 mL 10

FLH-R85130B-70Z 20 g 70 mL 16 FLH-R85130B-276F 100 g 276 mL 12

SiliaPrep™ AMPA SPE Cartridges Ordering Information

PN Sorbent weight Volume Qty / box PN Sorbent weight Volume Qty / box

SPE-R85130B-03G 200 mg 3 mL 50 SPE-R85130B-06S 1 g 6 mL 50

SPE-R85130B-03P 500 mg 3 mL 50 SPE-R85130B-06U 2 g 6 mL 50

SPE-R85130B-06P 500 mg 6 mL 50 SPE-R85130B-20X 5 g 25 mL 20

New to this Technology ? Our Kits Have Specially Been Designed for New UsersIf you wish to try this technology for the first time, we strongly suggest to try a SiliaMetS Metal Scavenger kit for screening purposes, since most sample matrices have different functionalities and affinities.

SiliaMetS NOVEL Metal Scavengers Kit Ordering Information

PN List of SiliaMetS included in kit Formats

K34530B AMPA, DEAM, DMT, Guanidine and Thiol 5 g, 10 g, 25 g, 50 g, 100 g (custom formats available)


SiliaMetS Metal Scavengers Portfolio

SiliaMetS / SiliaBond Structure Brief description Metals removed 1 Typical characteristics 2, 3

SiliaMetS Thiol

PN : R51030B Loading : ≥ 1.20 mmol/g Endcapping : Yes

SHSi

SiliaMetS Thiol is our most versatile and robust metal scavenger for a variety of metals under a wide range of conditions. It has been used in pharmaceutical processes up to production scale.

Ag, Hg, Os, Pd+2 & Pd0

Cu, Ir, Pb, Rh+1, Rh+2, Rh+3 & Sn

Color : White Density : 682 g/L Solvent Compatibility : 1 Prolonged Storage : 1 Shelf Life : 2 Years

SiliaMetS DMT


NH

Si N

NN

SH

SH SiliaMetS DMT is the silica - bound equivalent of 2,4,6 - trimercaptotriazine (trithiocyanuric acid, TMT). It is a versatile metal scavenger for a variety of metals and the preferred metal scavenger for ruthenium catalysts and hindered Pd complexes ( i.e. Pd( dppf )Cl2 ).

Ir, Ni, Os, Pd+2, Pd0, Pt, Rh+1, Rh+2, Rh+3 & Ru

Cd, Co, Cu, Fe, Sc & Zn

Color : Light brown Density : 732 g/L Solvent Compatibility : 1 Prolonged Storage : 1 Shelf Life : 2 Years

SiliaBond Amine


NH2Si

Better known for their electrophile scavenging efficiencies, and their base reagent qualities, SiliaMetS Amine, Diamine and Triamine are also proven scavengers for metals. They are very useful for scavenging Pd, Pt, Cr, W and Zn.

Cd, Cr, Pt, Rh+1 & Rh+2

Co, Cu, Fe, Hg, Pb, Pd+2, W & Zn

Color : Off - white Density : 700 g/L Solvent Compatibility : 1 Prolonged Storage : 3 Shelf Life : 2 Years

SiliaMetS Diamine


NH

SiNH2

Cr, Pd+2, Pd0, & Pt

Cd, Co, Cu, Fe, Hg, Ni, Pb, Ru, Sc, W & Zn


SiliaMetS Triamine


NH

SiHN

NH2

Cr, Pd+2, Pd0 & Pt

Ag, Cd, Co, Cu, Fe, Hg, Ni, Os, Pb, Rh+1, Rh+2, Rh+3, Ru, Sc, W & Zn


SiliaMetS AMPA


NSi P

PHO

HO

OH

OH

O

O

SiliaMetS AMPA is an aminomethylalkylphosphonic acid ligand known for its excellent metal - bonding properties. It is particularly efficient to remove Al, Sb, Ni, La, and also very effective for Co, Fe, Mn and Zn scavenging from reaction intermediates or final APIs.

Al, Ce, Dy, Er, Eu, Gd, Ho, La, Lu, Mn, Nd, Pm, Pr, Sb, Sm, Tb, Tm, V & Yb

Co, Cu, Fe, Ni & Zn

Color : Yellow Density : 707 g/L Solvent Compatibility : 1 Prolonged Storage : 3 Shelf Life : 1 Year

SiliaMetS Cysteine


NH

SiONa

SH

O

SiliaMetS Cysteine is the silica - bound equivalent of the amino acid cysteine. It is a versatile scavenger for a variety of metals and the preferred metal scavenger for tin residues. By attaching the molecule to the backbone via the amino group, the thiol group remains free and accessible for higher metal scavenging efficiency.

Cd, Fe, Ir, Os, Ru, Sc & Sn

Ca, Cr, Cs, Cu, La, Mg, Pd+2, Pd0, Pt, Rh+1, Rh+2 & Zn

Color : Orange Density : 665 g/L Solvent Compatibility : 2 Prolonged Storage : 3 Shelf Life : 1 Year

SiliaMetS DEAM


Si

NOH

OH

SiliaMetS DEAM is a versatile scavenger designed to remove trace metal of Ti, Zn, Fe and Ag as well as boronic acids from reaction intermediates or final APIs.

Ag, Fe, Sn, Ti & Zn

Color : Off - white Density : 679 g/L Solvent Compatibility : 1 Prolonged Storage : 3 Shelf Life : 1 Year

SiliaMetS Imidazole


NSi

N

SiliaMetS Imidazole is a versatile metal scavenger for a variety of metals including, Cd, Co, Cu, Fe, Ni, Pd, Os, and Rh, it is the preferred metal scavenger for iron catalysts.

Cd, Co, Cu, Fe, Ni, Os, W & Zn

Cr, Pd+2, Pd0, Rh+1 & Rh+2


SiliaMetS TAAcOH

PN : R69030B Loading : ≥ 0.41 mmol/g Endcapping : No

NSiN

N

OH (ONa)

OH (ONa)

OH (ONa)OH (ONa)

O

O

O

O

SiliaMetS TAAcOH & TAAcONa are supported versions of EDTA in their free and sodium salt forms. These two products are effective metal scavengers for Ca, Mg, Li, Ir, Cs, Os, Sn, Pd, Ni and Cu.

SiliaMetS TAAcOH is effective for metals in low or zero oxidation states, compared to SiliaMetS TAAcONa which is useful for metals in higher oxidation states (≥ 2).

Co, Ni, Os & Sc

Cr, Cs, Fe, Pd+2, Pd0, Rh+1, Rh+2 & Sn


SiliaMetS TAAcONa

PN : R69230B Loading : ≥ 0.41 mmol/g Endcapping : No

Ca, Cd, Cs, Cu, Fe, Ir, La, Li, Mg, Ni, Os, Rh+3, Sc, & Sn

Cr, Pd+2, Pd0, Rh+1, Rh+2 Ru, & Zn


SiliaMetS Thiourea


NH

Si NH

SSiliaMetS Thiourea is a versatile metal scavenger for all forms of palladium and is widely used in the pharmaceutical industry. Once complexed with a transition metal, it has been reported to be an effective catalyst.

Pd+2 & Pd0

Ag, Cu, Fe, Os, Rh+1, Rh+2, Rh+3, Sc & Sn


SiliaBond Tosic Acid

PN : R60530B Capacity : ≥ 0.54 meq/g Endcapping : Yes

SiS OH

O

O

SiliaBond Tosic Acid is in a class of strong acids used in different fields of synthetic organic chemistry. The aromatic ring makes it slightly more acidic than other supported sulfonic acids. It will not dissolve in methanol or any other solvents.

Fe, Rh & Sn

Ag, Cu, Ni, Pd, Pt, Ru & Zn


New Product

New Product

All SiliaMetS are made of standard 40 - 63 μm, 60Å silica gel, available in multi - ton scale. Other particle size distributions and pore diameters available on a custom basis.

1 The best scavenger for the removal of a particular metal is indicated in Blue while a good one is indicated in Orange.

2 Solvent Compatibility : 1: All solvents, aqueous and organic ; 2: All organic solvents.

3 Prolonged Storage : 1: Keep dry ; 2: Keep cool (< 8°C) under argon ; 3: Keep dry under argon.

Potentially Genotoxic Impurities (PGI) Scavenger - Contact Us for More Information

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SiliCycle Inc. Worldwide Headquarters2500, Parc-Technologique Blvd Quebec City (Quebec) G1P 4S6 CANADATel. : 1 418 874.0054 Toll Free : 1 877 745.4292 (North America only) Fax : 1 418 874.0355 www.SiliCycle.com [email protected]

Search by metalScavenger

SiliaMetS Thiol (Si-Thiol) PN : R51030B

SiliaMetS DMT (Si-DMT) PN : R79030B

SiliaBond Amine (Si-WAX) PN : R52030B

SiliaMetS AMPA (Si-AMPA) PN : R85130B

SiliaMetS Cysteine (Si-Cys) PN : R80530B

SiliaMetS DEAM (Si-DEAM) PN : R54430B

SiliaMetS Diamine (Si-DIA) PN : R49030B

SiliaMetS Imidazole (Si-IMI) PN : R79230B

SiliaMetS TAAcOH (Si-TAAcOH) PN : R69030B

SiliaMetS TAAcONa (Si-TAAcONa) PN : R69230B

SiliaMetS Thiourea (Si-THU) PN : R69530B

SiliaMetS Triamine (Si-TRI) PN : R48030B

Structure SHSi

NH

Si N

NN

SH

SH

NH2SiNSi P

PHO

HO

OH

OH

O

ONH

SiONa

SH

O

Si

NOH

OH

NH

SiNH2 NSi

N NSiN

N

OH (ONa)

OH (ONa)

OH (ONa)OH (ONa)

O

O

O

O

NH

Si NH

S

NH

SiHN

NH2

Loading mmol/g ≥ 1.20 ≥ 0.50 ≥ 1.20 ≥ 0.80 ≥ 0.30 ≥ 0.85 ≥ 1.28 ≥ 0.96 ≥ 0.41 ≥ 0.41 ≥ 1.07 ≥ 1.11

Met

als t

o be

scav

enge

d

AgAlCaCdCeCoCrCsCuFeHgIrLaLiMgMnNiOsPbPd (II)Pd (0)PtRh (I)Rh (II)Rh (III)Ru (II)ScSnTiWZn

A newcomer ? Our kits have been designed for maximum flexibility

PNK30730B Universal

Metal Scavengers Kit

K34530B Novel

Scavengers Kit

K34630B Palladium

Metal Scavengers Kit

Com

posi

tion

Si-Cysteine Si-DMT Si-Imidazole Si-TAAcOH Si-TAAcONa Si-Thiol Si-Thiourea Si-Triamine

Si-AMPA Si-DEAM Si-DMT Si-Guanidine Si-Thiol

Si-DMT Si-Diamine Si-Thiol Si-Thiourea Si-Triamine

PNK34730B

Tin Metal Scavengers Kit

K35230B Electrophile

Scavengers Kit

K32630B Nucleophile

Scavengers Kit

Com

posi

tion

Si-Cysteine Si-DEAM Si-DMT Si-TAAcOH Si-TAAcONa Si-Thiourea Si-Thiol

Si-Amine Si-Carboxylic Acid Si-DMAP Si-Diamine Si-Piperazine Si-TMA Acetate Si-Tosyl Chloride Si-Triamine

Si-Carbonate Si-DEAM Si-Diol Si-Guanidine Si-Isocyanate Si-Maleimide Si-Propylsulfonic Acid Si-Tosic Acid

Remember : All Kits are available in 5 g, 10 g, 25 g, 50 g, 100 g, and up to 1 kg formats Kits can easily be customized for any specific needs, contact us for more information.

SiliCycle offers an unparalleled range of Metal and Organic Scavengers, SiliaMetS®and SiliaBond®, to significantly facilitate any purification processes.

Typical procedure to be followed • Use 4-8 molar equivalent of Scavenger

• At room temperature up to 50°C

• Optimal pH range is from 2 to 10

• Typical solvents are THF, DMF, Ethyl Acetate, MeOH, PhMe, Ethers & Chlorinated solvents

• Stir one hour (1h) at moderate agitation (or more followed by ICP analysis)

TIP : Solution’s color might be a good indication of the scavenging progressDon’t forget to optimize via temperature, solvents, times, etc.

Could need some help ?Having a problem scavenging a product ?

Take advantage of SiliCycle’s expertise in scavenging. Our experienced R&D team can find the optimal conditions for you!

Our scavenging screening services are innovative as they provide an on-hand solution to quickly develop the most efficient metal or organic scavenging process for both time and cost savings.

Confidentiality is assured, as in most cases the solution involves working with API and other patented materials, and easy technology transfers are guaranteed.

Our team comprises passion driven scientists with various university levels in various specialities :

• Analytical, Inorganic, Organic & Organometallic Chemistry

• Biology & Biochemistry

• Catalysis

• Chemical Engineering

• Mesostructured Material

• Physical & Petrochemistry

22%

22% B.Sc.

Ph.D.

M.Sc.

R&DServices

Why are Potentially Genotoxic Impurities (PGI) Scavengers so important ?Genotoxic compounds induce genetic mutations and/or chromosomal rearrangements and can therefore act as carcinogenic compounds.

Whatever the nature of the impurity you might encounter, you can rely on our family of genotoxic Scavengers in order to eliminate tedious post-reaction purifications.

Search by chemicalScavenger

SiliaBond Amine (Si-WAX) PN : R52030B

SiliaBond Carbonate (Si-CO3) PN : R66030B

SiliaBond Carboxylic Acid (Si-WCX) PN : R70030B

SiliaMetS DEAM (Si-DEAM) PN : R54430B

SiliaMetS Diamine (Si-DIA) PN : R49030B

SiliaBond Diol (Si-Diol) PN : R35030B

SiliaBond DMAP (Si-DMAP) PN : R75530B

SiliaBond Guanidine (Si-GUA) PN : R68230B

SiliaBond Isocyanate (Si-ISO) PN : R50030B

SiliaBond Maleimide (Si-MAL) PN : R71030B

SiliaBond Piperazine (Si-PPZ) PN : R60030B

SiliaBond Propylsulfonic Acid (Si-SCX-2) PN : R51230B Tosic Acid (Si-SCX) PN : R60530B

SiliaBond TMA Acetate (Si-SAX2) PN : R66430B

SiliaBond Tosyl Chloride (Si-TsCl) PN : R44030B

SiliaMetS Triamine (Si-TRI) PN : R48030B

Structure NH2Si N+Si(CO3

2-)0.5 OHSi

OSi

NOH

OH

NH

SiNH2 OSi OH

OH NSi

N

NH

Si NH

N NSi C O NSi

O

O

NSi

NH

SSiOH

O

O

SiS OH

O

O

N+SiC3HC00-

SiS Cl

O

ONH

SiHN

NH2

Loading mmol/g ≥ 1.20 ≥ 0.46 ≥ 0.92 ≥ 0.85 ≥ 1.28 ≥ 0.97 ≥ 0.53 ≥ 0.80 ≥ 1.16 ≥ 0.64 ≥ 0.83 SCX-2 : ≥ 0.63 | SCX : ≥ 0.54 ≥ 0.71 ≥ 0.88 ≥ 1.11

Elec

trop

hile

s & N

ucle

ophi

les

to b

e sc

aven

ged

AcidAcid chlorideAcidic phenol

AlcoholAldehydeAlkoxideAmine

AnhydrideAniline

Boronic acid Carboxylic acid Chloroformate

HydrazineIsocyanate

KetoneOrganometallic

Sulfonyl chlorideThiol / Thiolate

ELECTROPHILE SCAVENGER : | NUCLEOPHILE SCAVENGER : | IONIC BONDING : | CATCH & RELEASE:

http ://www.silicycle.com/products/metal-scavengers

http ://www.silicycle.com/products/functionalized-silica-gels/siliabond-scavengers

Give our scavengers a try with SiliCycle MiniBlock® for mistake-proof parallel screeningsThe SiliCycle MiniBlock® platform offers full internal «flow-through» parallel processing of chemical reactions. The MiniBlock is unique in that reactions do not have to be removed from the apparatus for full processing but instead are run, partially purified and isolated in semi-crude form within the platform using a vertical flow design that is completely intuitive. Which is ideal for scavengers screening.

With our extensive experience in many niche areas, you are assured of a partner who is a leader in your domain.

BEST SCAVENGER : | GOOD SCAVENGER :

(COVALENT BONDING) (COVALENT BONDING)POS-001 v.1.2 02/15

© 2015, SiliCycle Inc.

Choosing your metal & organic scavenging solution

Why Silica outperforms Polymer-based resins ?• No Swelling

• Faster Kinetics

• Solvent Independent

• Easy to Use

• Mechanically Stable

• Thermally Stable

• Easily Scalable

• Flexible Formats

• Controlled Loading

SCX-2

SCX

7

All our Scavenging Solutions at a Quick GlanceWhich SiliaMetS Metal or SiliaBond Organic Scavenger will best suit your needs? Find out by ordering your FREE copy of our Scavenging Solution poster (PN : POS-001).

Call us to order your poster or for more information about our R&D Services : 1 877 745.4292 (North America only) +1 418 874.0054 (Worldwide)

R & D Services: Having a Problem with Your Scavenging or Metal Removal? We Can Help!Take advantage of SiliCycle’s expertise in scavenging. Our experienced R&D team can find the optimal conditions for you!

Our scavenging screening services are innovative as they provide an on - hand solution to quickly develop the most efficient metal or organic scavenging process for both time and cost savings.

Confidentiality is assured, as in most cases the solution involves working with API and other patented materials, and easy technology transfers are guaranteed.

Our team comprises passion driven scientists with various university levels in various specialities :

• Analytical, Inorganic, Organic & Organometallic Chemistry

• Biology & Biochemistry

• Catalysis

• Chemical Engineering

• Mesostructured Material

• Physical & Petrochemistry

With our extensive experience in many niche areas, you are assured of a partner who is a leader in your domain.

Custom R&D Services• Scavenging Screening• Catalysis Services• Organic Services• Chromatography, Purification &

Analytical Services• Material Science Services• Custom Packing Services

Heterogeneous Catalysis• Coupling (Suzuki,

Stille, Heck, Sonogashira, Kumada)

• Debenzylation• Hydrosilylation• Hydrogenation• Oxydation• Etc.

Scavenging Technology (Silica-Based)• Metal Scavengers• Electrophile Scavengers• Nucleophile Scavengers• Potential Genotoxic

Impurities (PGI)• Etc.

Sample Preparation• SPE Cartridges

and Well-Plates• Micro-SPE Tips• QuEChERS• Accesssories

(Vacuum Manifold, Collection Plates, …)

• Etc.

Organic Synthesis• Amide Coupling• Oxydation• Reductive Amination• Other Reagents Available

Analytical Chromatography• Spherical Silica Gels• HPLC and Guard Columns• HPLC Column Distributions

for Different Manufacturers• Etc.

Equipments• SiliCycle MiniBlock®

• TLC Scanner• Vacuum Manifold• Other Equipments

on Our Website

Chromatography• Irregular Silica Gels• Spherical Silica Gels for

Preparative Chromatography• Chromatographic Phases

(C18, NH2 …)

• Flash Cartridges and Accessories

• TLC Plates• Etc.

Consumables• Syringe Filters• Membrane Filters• Vials & Caps• Etc.

Other services available

WE PROVIDE SOLUTIONS TO THE GLOBAL CHEMICAL INDUSTRY.Founded in 1995, SiliCycle® Inc. is a worldwide leader in the development, the manufacturing and the commercialization of high value silica-based and specialty products for chromatography, analytical and organic chemistry. Our business extends to more than fifty countries and our customer portfolio includes companies in a wide range of markets.

At SiliCycle, we are at the forefront of the chromatography industry, owing to the extraordinary purity of our silica gels and polymeric sorbents, combined with our capacity to rapidly adapt our products to meet the specific requirements of scientists worldwide.

We lead the way in offering innovative first-rate UltraPure products. Our automated manufacturing processes are continuously optimized to ensure high purity and a low percentage of fine particles, thereby guaranteeing optimal performance. With our multi-ton manufacturing capacity, we are your partner of choice for all your analysis, metal removal, catalysis, synthesis, and purification requirements.

SiliCycle is also a leading service provider, offering turnkey solutions based on its expertise in organic chemistry, material science, analytical chemistry to name only a few. With state-of-the-art instrumentation in the areas of chromatography, spectroscopy, and manufacturing combined to an applications support laboratory, we are devoted to extend your R&D and make your project a success.

SiliCycle has several sales offices in many countries such as China, India, European Union (France & Germany) just to name a few. All products are available worldwide through SiliCycle or via distributors.

We are committed to providing you with the highest quality products and services in the industry

Information about SiliCycle is available at www.SiliCycle.com

SiliCycle Inc. Worldwide Headquarters2500, Parc-Technologique Blvd Quebec City (Quebec) G1P 4S6 CANADA Tel. : 1 418 874.0054 Toll Free : 1 877 745.4292 (North America only) Fax : 1 418 874.0355 www.SiliCycle.com [email protected]

SiliCycle China Chinese [email protected]

SiliCycle India Indian [email protected]

SiliCycle Europe European [email protected]

© 2015, SiliCycle Inc. Printed in Canada

AN - 002 v1.0 02/15

application note - silicyclelanthanides are widely used in organic synthesis and for a wide range of...

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