Date of Issue: 03/2015
Page 1 of 3
Magnesium Chloro 2,2,6,6-Tetramethylpiperidide
Lithium Chloride Complex (TMP-MgCl), typ. 20%
solution in THF / Toluene (typ. 1.0 M)
(Tetramethylpiperidinemagnesium Chloride
Lithium Chloride Complex)
PRODUCT
Magnesium Chloro 2,2,6,6-Tetramethylpiperidide Lithium Chloride Complex (TMP-MgCl), typ.
20% solution in THF / Toluene (typ. 1.0 M) (Tetramethylpiperidinemagnesium Chloride Lithium
Chloride Complex)
Product No. 408585
CAS-No. 215863-85-7
EINECS-No. not registered
FURTHER
INGREDIENTS
LiCl
CAS-No. 7447-41-8 EINECS-No. 231-212-3
THF
CAS-No. 109-99-9 EINECS-No. 203-726-8
Toluene
CAS-No. 108-88-3 EINECS-No. 601-021-003
APPLICATION
Selective deprotonation of arenes and heteroarenes.
Arenes and heteroarenes are typically deprotonated by a directed lithiation using
organolithium compounds or organolithiumamides (e.g. LDA). The high reactivity and
nucleophilicity of these reagents often result in unwanted side reactions and preludes the
presence of sensitive functional groups like esters or ketones. Additionally, such
deprotonation reactions often require low temperatures leading to higher production costs on
larger scale.
Due to their low kinetic basicity magnesiumamides tolerate a lot of functional groups but their
use is limited. It was shown by Prof. Knochel and his group that mixed Mg/Li complexes of the
type R 2 N-MgCl . LiCl exhibit a high solubility in THF as well as an enhanced kinetic basicity
and are perfect tools for selective deprotonation reactions. Best results are obtained when R =
tetramethylpiperidine is used.
Synthesis of highly substituted benzene derivatives 1 , e.g.:
The abov e details hav e been compiled to the best of our knowledge
on the basis of thorough tests and with regard to the current state
of our long practical experience. No liabilities or guarantees deriv ing
f rom or in connection with this leaf let can be imputed to us.
Reproduction, in whole or in part, only with our express permission.
® registrated trademark
www.rockwoodlithium.com
Europe:
Rockwood Lithium GmbH
Fax: +49 69 40126-72000
Americas:
Rockwood Lithium Inc.
Fax: +1 704 734-2718
Asia:
Rockwood Lithium Japan K.K.
Fax: +81-3-6434-5623
Product No. 408585, 401268
Date of Issue: 03/2015
Page 2 of 3
Regioselective synthesis of functionalized heteroarenes 2
1. B. W. Lin, O. Baron, P. Knochel, Org. Lett. 2006, 8, 5673,
2. A. Krasovskiy, V. Krasovskaya, P. Knochel, Angew. Chem. Int. Ed. 2006, 45, 2958
APPEARANCE
Brown to purple liquid
FORMULA
C 9 H 18 ClMgN * LiCl
PHYSICAL
PROPERTIES
Molecular weight:
TMP-MgCl 200.0
LiCl 42.4
Density:
0.97 g/ccm (23°C)
Boiling Point:
66 °C for THF
SPECIFICATION
assay of TMPMgCl (active base)
16 - 20 % (typ. 20 %, typ. 1.0 M)
LiCl
abt. 4 %, ratio TMP-MgCl/LiCl = 0.9 – 1.1 mol/mol
Solvent
Toluene abt. 10 %, THF abt. 66 %
The abov e details hav e been compiled to the best of our knowledge
on the basis of thorough tests and with regard to the current state
of our long practical experience. No liabilities or guarantees deriv ing
f rom or in connection with this leaf let can be imputed to us.
Reproduction, in whole or in part, only with our express permission.
® registrated trademark
www.rockwoodlithium.com
Europe:
Rockwood Lithium GmbH
Fax: +49 69 40126-72000
Americas:
Rockwood Lithium Inc.
Fax: +1 704 734-2718
Asia:
Rockwood Lithium Japan K.K.
Fax: +81-3-6434-5623
Product No. 408585, 401268
Date of Issue: 03/2015
Page 3 of 3
METHOD OF
ANALYSIS
Determination of assay as active base (Watson-Eastham titration); detailed description
available on request.
HANDLING
Organomagnesium compounds should only be handled under inert gas (nitrogen or argon).
Never add water, acids or oxidizing materials to the product. In case of fire use dry
extinguishers on basis of sodium chloride or limestone powder. Never use water or CO2 extinguishers. Pay attention to official Safety regulations (see also: 'Transport regulations' and
'Marking').
STORAGE
Product should be used in a closed apparatus under inert gas. Store in well ventilated areas
in tightly closed containers. As material decomposes slowly above room temperature
recommended storage temperature is below 20 °C.
TRANSPORT
REGULATIONS
UN-No.:
2924
Rail/Road (RID/ADR):
Class 3
PG II
Label 3 (8)
Sea (IMDG-Code):
Class 3
PG II
Label 3 (8)
Air (IATA-DGR):
Class 3
PG II
PAX 352
CAO 363
GHS HAZARD
PICTOGRAMS
H&P Phrases: See Safety Data Sheet
SIGNAL WORD
Danger
PACKING
Glass bottles of 100, 250, 500 and 1,000 ml.
Larger packaging on request.
TIME OF DELIVERY
3 - 4 weeks after receipt of order.
FURTHER
RELATED
DOCUMENTS
Lithium & Magnesium Amides, Safety Data Sheet.
The abov e details hav e been compiled to the best of our knowledge
on the basis of thorough tests and with regard to the current state
of our long practical experience. No liabilities or guarantees deriv ing
f rom or in connection with this leaf let can be imputed to us.
Reproduction, in whole or in part, only with our express permission.
® registrated trademark
www.rockwoodlithium.com
Europe:
Rockwood Lithium GmbH
Fax: +49 69 40126-72000
Americas:
Rockwood Lithium Inc.
Fax: +1 704 734-2718
Asia:
Rockwood Lithium Japan K.K.
Fax: +81-3-6434-5623