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Introduction 3

Aldrich

Haydn Boehm, Ph. D.

Global Marketing Manager: Chemical Synthesis

[email protected]

Dear Fellow Chemists,

Welcome to the third installment of Aldrich ChemFiles for 2011,

our complimentary quarterly innovation newsletter written by

experts from Aldrich Chemistry Product Management and R&D.

Our aim is to keep you informed of the new Aldrich Chemistry products that facilitate the

latest research methodologies and trends, and allow you to access key starting materials

and reagents more efficiently.

As well as introducing all the latest innovations across all of our product lines, in 2011 each

edition of Aldrich ChemFiles is themed to a product line. Aldrich ChemFiles Vol. 11, No. 3

will focus on our Synthetic Reagents product line. In this issue’s lead article, Troy Ryba,

Product Manager, highlights our new ChiroSolv® EnantioPrep™ Kits which define scalable,

optimized chiral resolution methods, to deliver pure enantiomers within a matter of days.Our “Synthetic Reagents” cover molecule is potassium carbobenzyloxycyanamide, which

is an efficient reagent for amine guanylation.

Aldrich ChemFiles Vol. 11, No. 3 will also introduce the latest innovations across all of our

product lines including new chiral catalysts and applications (Catalysis), chiral crotylsilanes

and EZ-CrotylMixes (Organometallics), halogenated pyridines and aldehydes (Building

Blocks), and new ionic liquids (Speciality Synthesis). I would also like to draw attention

to Aldrich’s new normality and molarity calculators (acid and base molarity/normality,

mass molarity, and solution dilution) which have been updated on our website at

Aldrich.com/calculator and are now available as iPhone® and iPad® applications.

We hope that Aldrich ChemFiles will enable you to expand your research toolbox

and advance your chemistry more effectively by implementing the latest innovative

synthetic strategies.Kind regards,

Dr. Haydn Boehm

Global Marketing Manager: Chemical Synthesis

Sigma-Aldrich Corporation

6000 N. Teutonia Ave.Milwaukee, WI 53209 USA

Editorial TeamHaydn Boehm, Ph.D.Wesley Smith

Dean Llanas

Sharbil J. Firsan, Ph.D.

Weimin Qian

Production Team

Cynthia Skaggs

Vincent Clark

Chris Lein

Tom Beckermann

Christian Hagmann

Denise de Voogd

Chemistry Team

Leslie Patterson, Ph.D.

Aaron Thornton, Ph.D.

Daniel Weibel, Ph.D.

Josephine Nakhla, Ph.D.

Ronaldo Mariz, Ph.D.

Pietro Butti, Ph.D.

Mark Redlich, Ph.D.

Troy Ryba, Ph.D.

Todd HalkoskiPaula Freemantle

Mike Willis

Aldrich ChemFiles Subscriptions

To request your FREE subscription to Aldrich ChemFiles visit

Aldrich.com/chemfiles or contact your local Sigma-Aldrich office

(see back cover).

Aldrich ChemFiles Online

Aldrich ChemFiles is also available in PDF format

at Aldrich.com/chemfiles.

Aldrich Chemistry Products

Aldrich brand products are sold through Sigma-Aldrich, Inc.

Sigma-Aldrich, Inc. warrants that its products conform to the

information contained in this and other Sig ma-Aldrich publications.

Purchaser must determine the suitability of the product for its

particular use. See reverse side of invoice or packing slip for addi-

tional terms and conditions of sale. All prices are subject to change

without notice.

To Place Orders or Contact Customer/Technical Services

Contact your local Sigma-Aldrich office (see back cover).

Aldrich ChemFiles (ISSN 1933–9658) is a publication of Aldrich

Chemical Co., Inc. Aldrich is a member of the Sigma-Aldrich Group.

© 2011 Sigma-Aldrich Co. LLC.

Volume 11, Number 3

Table of Contents

Synthetic Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

Catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

Organometallics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

Building Blocks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

Specialty Synthesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20

Stable Isotopes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22

Stockroom Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24

Labware Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26

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TO ORDER: Contact your local Sigma-Aldrich office (see back cover), or visit Aldrich.com/chemicalsynthesis.Aldrich.com

6

ChiroSolv® EnantioPrep™ Kits Deliver Pure

Enantiomers*

In 2007, Sigma-Aldrich began offering ChiroSolv Screening kits as useful

tools to identify the optimal chiral resolution conditions for racemates.

Very recently, Chirosolve, Inc. introduced ChiroSolv EnantioPrep Kits that

provide scalable, optimized chiral resolution methods and that deliver

pure enantiomers within a matter of days.

EnantioPrep is designed to obviate the obstacles analytical chemists face

during the elaborate process of diastereomeric crystallization. It offers

a well-established method to identify a comprehensive set of chiral

separation options, deliver pure enantiomers, and define a scalable chiral

separation. What sets EnantioPrep apart from other method development

tools is the inclusion of ChiroSolv Screening Kits that allow for 384 uniquereagent combinations to identify optimal separation conditions. It is an

extremely time and resource efficient approach to chiral resolution that

allows analytical chemists to skip over the hard part of finding an optimal

or scalable method to achieving an enantiopure product.

Key Features:

• Four Screening Kits offer exhaustive screening to identify best

separation conditions

• Purify Kits allow quick recovery of racemate

• Self-contained design of the product allows streamlined and consistent

process for method development and to get pure enantiomer

• Very little amount of racemate is needed (0.5–4 g)

• Results within 2 weeks; up to 90% of theoretical enantiomer yield

Key Benefits:

• Fast delivery of isolated enantiomer at a target purity and yield needing

minimal amount of racemate

• Cost-efficient method development through iterative crystallization

accelerates the lead optimization and preclinical studies

• Consistent results provide solid basis for developing complete

separation strategy

• Value-creating foundation builds differentiated patent estate

• Works with any racemate (acid, base, alcohol, aldehyde, ketone, amino

acid, racemate with multiple chiral centers)

How do ChiroSolv Solutions Work?

ChiroSolv EnantioPrep Kits use the method of diastereomeric crystal-

lization, a process that chemically separates enantiomers in a racemic

mixture by complexation with an enantiopure acid or base, resulting in

a mixture of diastereomeric salts. These salts have different chemical and

physical properties, which allow their separation. This well established

technology competes favorably with newer techniques such as asymmet-

ric synthesis, biocatalysis, enzyme resolution, kinetic resolution, or chiral

chromatography.

One major advantage of diastereomeric crystallization is that the proce-

dure scales up easily for manufacturing purposes. Today around 65% ofchiral products are made using this technique.

Examples:

• Paroxetine is a selective serotonin reuptake inhibitor developed by

Novo Nordisk’s subsidiary, Ferrosan, and licensed to GlaxoSmithKline. It

is sold as the hydrochloride salt under the name Paxil® for the treatment

of depression, anxiety, and obsessive–compulsive disorder. It is

prepared by resolution using (–)-di- p-toluoyl-L-tartaric acid.

• Setraline is an antidepressant that inhibits the uptake of serotonin in

the central nervous system and is sold by Pfizer under the name Zoloft®.

Diastereomeric crystallization of the racemate by (R)-mandelic acid is

used in its preparation.

• 2-Amino-5-methoxytetralin is an intermediate in the synthesis of

N-0923 (Nagase & Co., Ltd., Japan), a potent dopamine D2 receptor

agonist, effective against Parkinson’s disease (currently in clinical trial).

This intermediate is resolved by diastereomeric salt formation with

(S)-mandelic acid. The undesired isomer is then racemized and reused

in an iterative process.

• In the synthesis of AG-7404 (Pfizer), a key intermediate was resolved

by (–)-norephedrine. The final compound was obtained by the

combination of diastereomeric and enzymatic resolution.

How to Use ChiroSolv EnantioPrep Kits

Screen racemate against 384

separation conditions

Recover racemate using

recovery solution

Check purity

and yield

Heat, Cool

Repeat until targetenantiomeric purity

is achieved

Purify racemate using the

best separation condition

Extract purified

enantiomer ready

for testing

The experiment involves Three phases of work:

1. Screening: Racemate is screened against 384 different combinationsof resolving agents and solvents. When the combination of

the racemate, resolving agent, and solvent is heated together,

diastereomeric salt of one enantiomer preferentially crystallizes out

after cooling. The best combination of the reagent and solvent that

offers the highest yield and enantiomeric enrichment for the target

enantiomer is chosen to do further enrichment.

2. Recovery: After collecting all the material used during the screening

process, which includes the racemate, resolving agents, and the

solvents, this phase will treat it with our “recovery solution” that will

separate out the racemate from the resolving agents in the form of two







Ready to scale up? For competitive quotes on larger quantities or custom synthesis, contact your local Sigma-Aldrich office, or visit safcglobal.com.

7Synthetic Reagents

liquid layers. Using separatory funnel, these layers will be separated and

the racemate (typically > 90%) will be recovered from the bottom layer

3. Purification: The goal of this phase is to identify how many

recrystallization steps are required to get the enantiomeric purity

needed. The end result should be a smaller quantity of enriched

enantiomer (maximum yield: about 35% of the total racemate given).

EnantioPrep allows scientists to:

• Quickly screen a racemate against a comprehensive list of 384 resolving

agent/solvent combination to identify all possible resolution conditions

• Recover the used racemate and proceed to purify it until target purity

is achieved

• Define a step-by-step resolution method that can be scaled up to kilo

quantities

This purification solution can be used for racemic acids, bases, alcohols,

amino acids, aldehydes, and ketones.

EnantioPrep includes a set of four Acid or Base Series Screening Kits,

Recovery Solution for acid or base racemate that recovers up to 90%

racemate used during screening; and a self-contained Purification Package

that allows incremental purification of enantiomer through simple steps.

Example Kit.

Each individual screening kit is in a disposable, ready-to-use, 96-vial,

high-throughput format that allows the entire analysis to be performed

inside the kit without removing any vials. The kit is made of polypropylene

material that can withstand extreme temperatures (–20 to 120 °C),

allowing the entire kit to be placed in a hot-water or ice bath without

damage. The set of four screening kits offers unique 384 combinations of

resolving agent/solvent combinations, so that a full set of separation

conditions can be identified early on to help the rest of the research.

Resolving agents are chosen with manufacturing use in mind; they are

relatively inexpensive and recoverable in high yield after the resolution is

complete. The high-throughput format allows scientists to explore the

separation conditions in parallel and get results within 24 hours, which

may otherwise take over two months.

When the Recovery Solution is added to the diastereomeric salts of the

racemate and the resolving agents, it breaks the diastereomeric salt intoneutral racemate that goes in the organic layer; while the resolving agents

stay in the aqueous layer. Separating these two layers and removing the

residual solvents from the organic layer returns the original racemate.

The Purification Package includes a filter funnel with vacuum adapter,

enantiomer and filtrate collection bottles, spare filters, and pH paper.

After recovering the racemate from Screening Kits (using the Recovery

Solution), the resolving agent and solvent combination associated with

best separation condition is selected to get incrementally purified salt

of the target enantiomer until the required purity is achieved. Finally the

enantiomer is extracted from the diastereomeric salt. In our experience, if

you use 5 g of racemate during purification, depending on the number of

recrystallization steps needed, you can get up to 2 g of pure enantiomer. The entire purification typically requires up to eight hours of hands-on

work giving results within one week.

Types of Kits

Acid

The acid screening kits include a distinct group of chirally pure acids and

is used to resolve racemic bases and amino acids (some pre-processing is

required for amino acids). Examples of resolving agents in the acid kits are:

• (–)-Camphoric acid

•(+)- and (–)-Camphorsulphonic acid

• (+)- and (–)-Dibenzoyltartaric acid

• (–)-Malic acid

• (+)- and (–)-Mandelic acid

• (+)-Lactic acid

• (+)- and (–)-Tartaric acid

Base

The base screening kits include a distinct group of chirally pure bases or

amines, and is used to resolve racemic acids, alcohols, aldehydes, and

ketones (some pre-processing is required for the latter three). Examples of

resolving agents in the base kits are:

• (–)-2-Aminobutanol

• (–)-Brucine

• (–)-Cinchonidine

• (+)-Cinchonine

• (+)-Dehydroabietylamine

• (+)- and (–)-Methylbenzylamine

• (+)-Quinidine

• (–)-Quinine

http://www.safcglobal.com/





8

Case Studies with ChiroSolv®

EnantioPrep™ Solution

ChiroSolv EnantioPrep kits were used fortwo sample racemates:

• N -Benzyl-1-(4-methylphenyl)propane-2-amine (racemate had

70% S and 30% R isomer). Goal was to get over 90% purity for R isomer.

This racemate was resolved by di-tolyltartaric (+) acid in 100% IPA.

Case Study Results

Racemate Desired isomer purity Starting material Amount recovered # of recrystallization Amount of pure enantiomer

N -Benzyl-1-(4-methylphenyl)propane-2-amine R isomer, >90% purity 1.046 g 0.996 g (95%) 4 280 mg

N -Benzyl-1-(4-benzylphenyl)propane-2-amine R isomer, >90% purity 1.931 g 1.738 g (90%) 3 700 mg

After two recrystallizations, we were able to obtain 30% S and 70% R.

Additional two recrystallizations yielded > 90% enrichment in R. Theyield was over 90% of theoretical value.

• N -Benzyl-1-(4-benzylphenyl)propane-2-amine (racemate had

50% S and 50% R). Goal was to get over 90% purity of the R isomer. This

racemate was resolved by S-acetylmandelic acid (+) in 90% IPA. After

two recrystallizations, we were able to obtain 80% R and 20% S, with

yield over 80% of theoretical value.

Representative Scope

DBU,Et3N 3HF, or Et3N 2HF* promoters:

R OH

XtalFluor-E or -M+ promoter *

substrates products

R H

O

R R

O

R OH

O

RS

O

CH3

R F

R H

R R

R F

O

RS F

F F

F F

O

OHRO

RO

RORO O

FRO

RO

RORO

XtalFluor reagents are crystalline dialkylaminodifluorosulfinium

tetrafluoroborate salts. They are useful for the deoxofluorination

of hydroxyl and carbonyl moieties when used in conjunction with apromoter.*

Advantages of XtalFluor salts

Aldrich XtalFluor Reagents

H3C

H3C N=SF2 BF4

– –

ON=SF

2 BF

4

+ +

719439 719447

XtalFluor-E® XtalFluor-M®

XtalFluor-E and XtalFluor-M are registered trademarks of OmegaChem Inc.

Multi-kilogram quantities available through Manchester Organics

Looking for a Safer

Fluorinating Reagent?

Aldrich.com/xtalfluors

References: (1) Beaulieu, F. et al. Org. Lett. 2009, 11, 5050. (2) L’Heureux, A. et al. J. Org. Chem.

2010, 75, 3401.

• Air-stable solids

• Enhanced thermal stability over

DAST and other structurally similar

deoxofluorination reagents

• Broad substrate scope

• Predictable and high

chemoselectivity

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10

Recap: How to Use ChiroSolv® Kits

1. Choose the right kit type (Acid Series 1, 2, 3, 4 or Base Series 1, 2, 3, 4)

depending on the identity of the racemate.

2. If the racemate is an alcohol, amino acid, aldehyde or ketone, you may

need to pre-process the racemate.

3. Add 0.03 mmol of your racemate to each of the 96 vials. Depending on

the availability of the dispensing autostation and the racemate. type

(liquid or powder), you may need to remove the seal on the vials. Note

the seal is pierceable to accommodate direct injection of racemate by

liquid dispensers.

4. In an oven or water bath, heat the rack along with its vials to 80 °C

(optimal temperature for most of these experiments) or until the

mixture becomes homogeneous.

5. Allow the kit to cool to ambient temperature. If required, further

cool it to 4 °C or 0 °C to observe crystallization. Vials with crystals are

considered positive results and should be examined further.

6. Often, more vials with positive results can be obtained using standard

crystal initiation techniques. Vials with no crystals even after this effort

are considered negative results.

7. Separate out the positive test results and note their alphanumeric

identification.

8. Liberate the enantiomers from their diastereomeric salts and analyze

by optical rotation. Typically, only one or two vials will show maximal

optical purity.

Features

• Eight types of ready-to-use disposable kits providing a total of 768

resolving agent–solvent combinations.• Very little amount of racemate required (less than 3 mmol per kit).

• Concentrations of the resolving agents are calibrated to give accurate

results and optimal crystallization.

• Pierceable seal allows easy racemate dispensing; vials held together by

a plastic ring so that vials can be picked up and inspected together for

crystal formation.

• Easy to follow, step-by-step instructions and results charts.

• Conveniently designed for easy robotic manipulations.

• Kits and vials have unique identification (barcode or alphanumeric) for

cross-referencing.

• Long shelf life at room temperature (2 years).

Each rack has aunique barcode.

Each vial contains aunique combination of

resolving agent/solvent—8 types of kits give 768 such

combinations.

Pierceable septa or foilseal for easy

robotic manipulation.

Plastic sleeve holdsthe vials together evenwhen they are out of

the rack.

Each vial has a uniquealphanumeric identification.

Rack, vials, and septaare chemically inertand can withstand–20 °C to 120 °C.

Extra septum matprovided in kits for

solid racemates.

Product Information for Liquid RacematesProduct No. Product Name/Description

681431 ChiroSolv Resolving Kit, Acid Series 1


681415 ChiroSolv Resolving Kit, Acid Series 3699217 ChiroSolv Resolving Kit, Acid Series 4

700363 ChiroSolv Resolving Kit, Complete Acid Series

681407 ChiroSolv Resolving Kit, Base Series 1




700371 ChiroSolv Resolving Kit, Complete Base Series

Product Information for Solid Racemates

Product No. Product Name/Description





700398 ChiroSolv Resolving Kit, Complete Acid Series





700401 ChiroSolv Resolving Kit, Complete Base Series

For more information, please visit Aldrich.com/chirosolv

Synthetic Reagents

Kits: A1, A2, A3, A4 or B1, B2, B3, B4

Analyze selected vialswith crystals for

specific rotation

Select vials with crystals &note their alphanumeric

identification

Unknown Racemate

Cool mixture 4 °C to 0 °C Yes

No

Cool mixture to ambient temp.

Heat mixture to 80–100 °C

Ready to Use Disposable Kit























http://www.aldrich.com/chirosolv

http://www.aldrich.com/chirosolv

























Need a MolarMatic™

Measuring Cylinders

for your Acid solutions?

Aldrich MolarMatic Measuring Cylinder

Our MolarMatic graduated measuring cylinder allows you to

add concentrated acid to the desired molarity line. Simply pour

the measured acid into one liter of water, and your 1 M, 2 M, or

3 M solution is prepared.

• No calculations

• No struggling for the correct cylinder

Convenient Dual-Scale Graduated Cylinder

• Class A, 350-mL cylinders

• Graduated in 5.0-mL increments; calibrated "to deliver"

• 1 to 3 Molar scale on opposite side

• Eliminates repetitive molar calculations and potential errors

• Set contains one of each cylinder in plastic storage case

Acid Type Cat. No.

Acetic acid Z683728

Hydrochloric acid Z683736

Nitric acid Z683744

Sulfuric acid Z683752

Set of four Z683760

Save time. Add Aldrich.

Aldrich.com/molarmatic

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20

Specialty SynthesisPietro Butti, Ph.D.

Product Manager

[email protected]

Ionic Liquids: A Smart Alternative

Environmentally low-impact alternatives, sustainable processes, industrial

ecology, and efficiency are some of the topical words which are directing

the development of the new generation of technologies and products.1

Therefore, the importance of compounds coming from renewable feed-

stock or enabling high levels of recycling is growing exponentially. These

compounds are seen as promising materials able to replace compoundsproduced with fossil fuel sources, hence reducing our global dependence

upon them.2

NNR' R'' N

R

R

NR'''

R'

R''

R

PR'''

R'

R''

Figure 1: Commonly used ionic liquids aprotic cations.

NTf2

PF6

BF4

OTf

CH3COO

NO3 Br

CF3COO

Cl

Water Miscibility

Figure 2: Commonly used ionic liquids aprotic anions.

Ionic liquids have been recognized and developed by scientists fromacademia and the chemical industry as new green(er) chemicals.3 Even if

they are not always the “greenest choice”, 4 ionic liquids, a group of salts

that exist as liquids at relatively low temperatures (<373 °K) (Figures

1 and 2), have gained overwhelming interest over the past decades

(Chart 1). They offer unique sets of properties, often difficult to achieve

with any other compounds. Some of these properties are chemical and

thermal stability, non-flammability, and low vapor pressures.5

0

500

1000

1500

2000

2500

3000

3500

4000

4500

5000

1 9 9 0

1 9 9 1

1 9 9 2

1 9 9 3

1 9 9 4

1 9 9 5

1 9 9 6

1 9 9 7

1 9 9 8

1 9 9 9

2 0 0 0

2 0 0 1

2 0 0 2

2 0 0 3

2 0 0 4

2 0 0 5

2 0 0 6

2 0 0 7

2 0 0 8

2 0 0 9

2 0 1 0

Year

N u m b e r o f P u b i c a t i o n s

Chart 1: Number of SciFinder ® hits containing the words “Ionic Liquids” from 1990 to

2010. Red total number of publications, Gray filtered through patent applications.

This class of compounds opens up a variety of opportunities in many dif-

ferent applications. For example, chemical processing and fine chemicals

synthesis such as the BASIL™ process (Scheme 1).6

N

NR2PCl

EtOH N

H

N

Cl-+ +R2POEt

Recycle

Scheme 1: Preparation of alkoxyphenylphosphines (R2POEt) with the BASIL process.6

Another example is the olefin metathesis, published by Grela and

co-workers in 2007 (Scheme 2).7

TsNTs

N

H2C CH2CH3 CH3

O

Ru

CH3

H3C

Cl

Cl

NMesMesN

N

PF6

Up to >98% Conversion5 Cycles

5 mol%,

BMIM

PF6 (70956)Tol, 3h, 25°C

Scheme 2: Recyclable catalytic system for a model metathesis reaction.7

Ionic liquids are also used in polymer and biopolymer processing as

enabling technology to utilize cellulose.1,8 In electrochemical applications

and in metal processing9 they offer unprecedented prospects for metal

deposition. Furthermore, they can be used in nuclear fuel processing. 10

They lead to new opportunities in separation processes, or their tune-

able properties can be exploited to prepare engineering fluids or other

high-performance materials. Ionic liquids are also used in analytical

chemistry11 (Supelco’s GC capillary column SLB-IL series) and biomedical

applications.12

These examples highlight just a few of the large number ofpotential applications in which this class of extraordinary compounds can

be used.

Publications per Years



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22

Aldrich NMR Solvents

Challenge Us… And See Why Our Quality isUnsurpassed!

High quality NMR solvents are essential for satisfying the most rigorous

demands of NMR-based research and analyses. At Aldrich, we are pas-

sionate about providing this high level of quality to our customers andwork continuously to meet these requirements. We offer the widest

range of NMR solvents with the highest isotopic enrichment available

along with excellent chemical purity. We consistently review and im-

prove our methods for solvent purification and for the reduction of water

content in our already high quality NMR solvents. All of our NMR solvents

undergo thorough quality control testing during the manufacturing and

packaging processes to verify the product quality is preserved.

Most deuterated NMR solvents readily absorb moisture. To minimize the chance ofwater contamination, use carefully dried NMR tubes and handle NMR solvents in adry atmosphere.

How to Obtain a Nearly Moisture-free Surface

1. Dry glassware at ~150 °C for 24 hours and cool under an inert atmosphere.

2. Rinse the NMR tube with the deuterated solvent prior to preparing the sample. This allows for a complete exchange of protons from any residual moisture onthe glass surface.

3. For less demanding applications, a nitrogen blanket over the sample prepara-tion setup may be adequate.

How to Avoid Sources of Impurities and Chemical Residues

1. Use clean, dry glassware and PTFE accessories.

2. Use a vortex mixer instead of shaking the tube contents. The latter action canintroduce contaminants from the NMR tube cap.

3. Residual chemical vapor from equipment can be a source of impurities;residual acetone in pipette bulbs is a common example.

How to Remove Solvent Residue

1. Protonated solvent residue can be removed by co-evaporation.

2. Use a small quantity of the desired deuterated solvent, a brief high vacuumdrying (5–10 min), and then prepare the NMR sample.

3. Solvents such as chloroform-d, benzene-d6, and toluene-d8, also removeresidual water azeotropically.

How to Avoid TMS Evaporation

1. Extended storage of TMS-containing solvents can lead to some loss of TMS.Storing these solvents in Sure/Seal™ bottles virtually eliminates such a loss. *

2. Purchase TMS-containing solvents in single-use ampules.

* To dispense the product from Sure/Seal™ bottle or septum vials, use standardsyringe needle techniques. For details and recommended procedures, pleaserefer to Aldrich Technical Bulletin AL-134 or visit our Web site at Aldrich.com.

Use and Handling of NMR Solvents

Aldrich Chemistry also offers unparalleled convenience and service. Our

award-winning website allows for quick product searching, easy ordering,

and a wealth of valuable tools and information to aid your research efforts.

We also offer on-site stocking programs for NMR solvents so they are avail-

able to you for immediate use. If you have technical questions, you can

feel comfortable knowing our knowledgeable and well-trained technical

service specialists can answer your toughest questions.

Try our NMR Solvents today to see their high quality for yourself.

For a complete listing of all NMR-related products and information,

visit Aldrich.com/nmr

Stable IsotopesLeslie Patterson, Ph.D.

Product Manager

[email protected]




http://www.aldrich.com/nmr

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2Stable Isotopes

Specialty NMR Solvents

Aldrich Chemistry offers a wide range of high purity deuterated solvents

for the NMR community. In addition, we also offer various specialty

solvents for more demanding applications. Whether you need the high-

est enriched deuterium oxide available, or solvents with a reduced HOD

peak, we have what you need.

“Special HOH” Solvents

When customers requested NMR solvents with a suppressed HOD peak

we listened, and developed NMR solvents called “Special HOH”. These

solvents have an HOD peak which is less than 1% of the HOH peak, to

minimize potential exchange with an analyte. “Special HOH” solvents also

meet our standard water specification for NMR solvents.

1H-NMR Spectrum of DMSO-d6 “Special HOH”

Anhydrous NMR Solvents

When water content is of paramount concern, try our anhydrous

solvents that contain reduced levels of water.

“Extra” Enriched D2O

With an enrichment of 99.994 atom % D, this is the highest enriched

deuterium oxide available.

For additional information visit Aldrich.com/nmr

or contact:

Stable Isotope Technical Service

Phone: (937) 859-1808

(800) 448-9760 (US and Canada)

Fax: (937) 859-4878

E-mail: [email protected] 1 1. 5 11 .0 1 0. 5 10 .0 9 .5 9 .0 8 .5 8 .0 7 .5 7 .0 6 .5 6 .0 5 .5 5 .0 4 .5 4 .0 3 .5 3 .0 2 .5 2 .0 1 .5 1 .0 0 .5 0 .0 – 0. 5

ppm

2 .5 2 .4ppm

3.3

ppm

HOH

DMSO-d6residual peak

HOD

Deuterium oxide, Extra, 99.994 atom % D

613398-10G serum bottle 10 g

613398-50G serum bottle 50 g

Acetonitrile-d3, 99.8 atom % D, Anhydrous (water < 10 ppm)

569550-10X1ML ampule 10 x 1 mL

Benzene-d6, 99.6 atom % D, Anhydrous (water < 10 ppm)

570680-50G glass bottle 50 g

Chloroform-d, 99.8 atom % D, Anhydrous (water < 10 ppm)


Dimethyl sulfoxide-d6, 99.9 atom % D, Anhydrous (water < 50 ppm)


569585-5X1ML ampule 5 x 1 mL569585-10X1ML ampule 10 x 1 mL

Methanol-d4, 99.8 atom % D, Anhydrous (water < 50 ppm)




Toluene-d8, 99.6 atom % D, Anhydrous (water < 10 ppm)


Acetonitrile-d3, 99.8 atom % D, "Special HOH"




Dimethyl sulfoxide-d6, 99.9 atom % D, "Special HOH"




716731-10x0.75ML ampule 10 x 0.75 mL

716731-10ML serum vial 10 mL

716731-50ML serum vial 50 mL

Data acquired on a Varian 400 MHz instrument.



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24

Stockroom Reagents Todd Halkoski

Market Segment Manager, Solvents and Reagents

[email protected]

Sigma-Aldrich® is a Leading Global Supplier and

Manufacturer of High Quality, Stockroom and

Essential Research Products

We specialize in providing the most comprehensive product range

and widest selection of purity grades to fulfill your particular

application needs.

• Solvents — As a leading supplier of high-purity, research grade

solvents, we have the solvent to meet your exact needs

• Acids and Bases — From ACS grade to TraceSELECT® Ultra for the ultra

trace analysis level down to ppb and ppt.

• Routine Organic and Inorganic Reagents

• Adsorbents, Filter Aids, and Drying Agents

You will also find several programs that offer unique solutions to help

control your costs. One may be right for you!

National Association of Scientific Materials

Managers (NAOSMM)

Sigma-Aldrich is a proud partner of NAOSMM and its members receive

savings on a wide range of Sigma-Aldrich Chemistry products.

Supply Rewards™ Program

Get rewarded for choosing Sigma-Aldrich. Earn rewards for your team,

your community, or yourself, every time you purchase selected products

from Sigma-Aldrich. With over 1,500 eligible common laboratory products

to choose from, earning reward points couldn' t be easier.

New Lab Start-Up Program

Get your new lab set up in an easy and economical way.

Your lab is eligible for the program if:

• You are starting a new lab

• You are moving to a new location

• You have received your first research grant

To learn more, visit Aldrich.com/stockroom

By always listening, Sigma-Aldrich delivers.Monthly Savings from Sigma-Aldrich

Easy-to-find site offers monthly savings on Chemistry, Life

Science, Analytical, and Labware products.

United States

Aldrich.com/offers

Europe

Aldrich.com/offerseu

For specific country discounts,

visit us at Aldrich.com

The Sigma-Aldrich Pressure-Temperature Nomograph allows you to

quickly and easily estimate boiling points at various pressures.

Interactive controls simplify calculations to improve the efficiency of your

distillation or evaporation process.

Pressure Conversion Tab: Use the built-in Pressure Conversion Calculator

to convert among five units of pressure using either numeric values or

scientific notation.

Temperature Conversion Tab: Quickly calculate temperature conversions

without leaving the Nomograph.

Printable: Need a hard copy to take with you? Simply right-click and

select 'print'.

Aldrich.com/nomograph

Stockroom Reagents



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Need a MolarityCalculator foryour Acid/Basesolutions?

Aldrich Normality and Molarity Calculator

Features

• Calculates molarity for known acids and bases• Calculates solutions of a solid reagent

• Dilutes a solution of known molarity

• Gets results at the click of a button

• Runs on your iPhone® and iPad® mobile digital devices

Benefits

• Saves time over hand calculations

• Increases accuracy of calculations

Easy-to-Use

1. Select Acid or Base from drop down menu

2. Density, FW, and Wt. % will auto-populate

3. Input desired volume and concentration

4. Click on “Calculate”

Add Aldrich to save time and access the

Normality and Molarity Calculator at

Aldrich.com/calculator

iPhone and iPad are trademarks of Apple Inc., registered in the US and other countries. 76070







26

Labware NotesPaula Freemantle

Product Manager

[email protected]

Aldrich® Rotary Evaporator Replacement

Glassware

• Cross-referenced with Buchi part numbers

• Plastic-coated and uncoated versions

• Jointed flasks compatible with most evaporators

This heavy-duty glassware is designed to fit Buchi rotary evaporatorsand is cross-referenced with Buchi part numbers to aid in selection. The

condensers and flasks are available in non-coated glass for maximum

resistance to solvents and heat, and with poly coating for extra protection

from breakage. The jointed flasks and splash-guard adapters will fit most

brands of rotary evaporators. Note that 35/20 and 35/25 spherical joint

components are interchangeable.

Premium quality glassware, widest range, low cost

• Condenser Assemblies and Components

• Drying Flasks with Indents

• Evaporating Flasks, Pear-Shape

• Large Evaporator Flasks

• Receiving Flasks Adapters

• Receiving Flasks

• Splash Guard Adapters

• Vapor Duct Tubes

To see the complete range of products or to place orders,

visit Aldrich.com/evapglass

Z682055

Z515515

Z549193

Z682187

Z682713

Z682829

Z682918

Z682411



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2Labware Notes

News and Innovation

Aldrich® FKM sleeve stopper septa

These new septa are made from fluoroelastomer FKM which is highly

resistant to a broad range of solvents. An elastomer study done at

Sigma-Aldrich compared the solvent compatibility (resistance) of FKM

and EPDM rubber (Figure 1). A Sealability Factor was determined

for each elastomer. The lower the number the more compatible the

rubber is with a solvent.

Z569941 10/30 joints

Z569968 14/20 joints, 2, 4, and 8 oz Aldrich bottles

Z569976 15/25 joints, 10, 32, 40 oz, 1 L Aldrich bottles,

125 mL, 1 L Sure/Seal bottles

Z569984 24/40 joints, 64, 80 oz, and 1 gal Aldrich jugs

Aldrich Rotary Evaporator Adapter Set

This versatile adapter connects jars and bottles to the vapor tube of a rotary

evaporator. Precision machined from durable, chemically inert glass-filled

PTFE. The unique, “universal fit” threaded connection adapts to any suitable

cap. Simply insert the threaded shaft of the adapter through a 16 mm diam-

eter holed cap and secure by hand-tightening the PTFE gasket and nut.

Attach the other end of the adapter to the vapor tube via standard taper

joint and clip. Set includes one 58 x 400 mm diameter holed cap and a solid

top cap with PTFE liners, and a 200 mL borosilicate glass jar.

Z723169-1EA 24/40 joint

Z723177-1EA 29/32 joint

Julabo® Economy Series

Refrigerated/Heating

Circulators

• Compact design

• Temp. range -20 to 100 °C

• 0.35 bar pump pressure

• 15 L/min pump flow

• Cooling capacity 120 W, at 0 °C

• 200 W, at 20 °C

• Heater capacity 2 kw

• Bath opening W × L × D

15 cm × 16 cm × 13 cm

• Overall W × L × H20 cm × 36 cm × 56 cm

• Volume 4.5 L

Z557285-1EA 115 VAC

Z653209-1EA 230 VAC

Figure 1

Sealability Factor The lower the number the higher the compatibility

0

500

1000

1500

2000

25003000

3500

4000

4500

D i e t h y l e t h e r

D i c h l o r o m e t h a n e

B e n z e n e

C y c l o h e x a n e s

D i i s o p r o p y l a m i n e

Fluoroelastomer FKM

EPDM rubber

























Sigma-Aldrich

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